《海相碳酸盐阴极发光性的控制因素》2008020135 彭博

01/2008:20223 2.2.23. ATOMIC ABSORPTION SPECTROMETRY GENERAL PRINCIPLEAtomic absorption is a process that occurs when a ground state-atom absorbs electromagnetic radiation of a specific wavelength and is elevated to an excited state. The atoms in the ground state absorb energy at their resonant frequency and the electromagnetic radiation is attenuated due to resonance absorption. The energy absorption is virtually a direct function of the numberof atoms present.This chapter provides general information and defines the procedures used in element determinations by atomic absorption spectrometry, either atomisation by flame, by electrothermal vaporisation in a graphite furnace, by hydride generation or by cold vapour technique for mercury.Atomic absorption spectrometry is a technique for determining the concentration of an element in a sample by measuring the absorption of electromagnetic radiation by the atomic vapour of the element generated from the sample. The determination is carried out at the wavelength of one of the absorption (resonance) lines of the element concerned. The amount of radiation absorbed is, according to the Lambert-Beer law, proportional to the element concentration.APPARATUSThis consists essentially of:a source of radiation;a sample introduction device;a sample atomiser;a monochromator or polychromator;a detector;a data-acquisition unit.The apparatus is usually equipped with a background correction system. Hollow-cathode lamps and electrodeless discharge lamps (EDL) are used as radiation source. The emission of such lamps consists of a spectrum showing very narrow lines with half-width of about 0.002 nm of the element being determined.There are 3 types of sample atomisers:Flame techniqueA flame atomiser is composed of a nebulisation system with a pneumatic aerosol production accessory, a gas-flow regulation and a burner. Fuel-oxidant mixtures are commonly used to produce a range of temperatures from about 2000 K to 3000 K. Fuel gases include propane, hydrogen and acetylene; air and nitrous oxide are used as oxidants. The configuration of the burner is adapted to the gases used and the gas flow is adjustable. Samples are nebulised, acidified water being the solvent of choice for preparing test and reference solutions. Organic solvents may also be used if precautions are taken to ensure that the solvent does not interfere with the stability of the flame.Electrothermal atomisation techniqueAn electrothermal atomiser is generally composed of a graphite tube furnace and an electric power source. Electrothermal atomisation in a graphite tubefurnace atomises the entire sample and retains the atomic vapour in the light path for an extended period. This improves the detection limit. Samples, liquid as well as solid, are introduced directly into the graphite tube furnace, which is heated in a programmed series of steps to dry the sample and remove major matrix components by pyrolysis and to then atomise all of the analyte. The furnace is cleaned using a final temperature higher than the atomisation temperature. The flow of an inert gas during the pyrolysis step in the graphite tube furnace allows a better performance of the subsequent atomisation process.Cold vapour and hydride techniqueThe atomic vapour may also be generated outside the spectrometer. This is notably the case for the cold-vapour method for mercury or for certain hydride-forming elements such as arsenic, antimony, bismuth, selenium and tin. For mercury, atoms are generated by chemical reduction with stannous chloride or sodium borohydride and the atomic vapour is swept by a stream of an inert gas into a cold quartz cell mounted in the optical path of the instrument. Hydrides thus generated are swept by an inert gas into a heated cell in which they are dissociated into atoms.INTERFERENCESChemical, physical, ionisation and spectral interferences are encountered in atomic absorption measurements. Chemical interference is compensated by addition of matrix modifiers, of releasing agents or by using high temperature produced by a nitrous oxide-acetylene flame; the use of specific ionisation buffers (for example, lanthanum and caesium) compensates for ionisation interference; by dilution of the sample, through the method of standard additions or by matrix matching, physical interference due to high salt content or viscosity is eliminated. Spectral interference results from the overlapping of resonance lines and can be avoided by using a different resonance line. The use of Zeeman background correction also compensates for spectral interference and interferences from molecular absorption, especially when using the electrothermal atomisation technique. The use of multi-element hollow-cathode lamps may also cause spectral interference. Specific or non-specific absorption is measured in a spectral range defined by the band-width selected by the monochromator (0.2-2 nm).BACKGROUND CORRECTIONScatter and background in the flame or the electrothermal atomisation technique increase the measured absorbance values. Background absorption covers a large range of wavelengths, whereas atomic absorption takes place in a very narrow wavelength range of about 0.005-0.02 nm. Background absorption can in principle be corrected by using a blank solution of exactly the same composition as the sample, but without the specific element to be determined, although this method is frequently impracticable. With the electrothermal atomisation technique the pyrolysis temperature is to be optimised to eliminate the matrix decomposition products causing background absorption. Background correction can also be made by using 2 different light sources, the hollow-cathode lamp that measures the total absorption (element + background) and a deuterium lamp with a continuum emission from which the background absorption is measured. Background is corrected by subtracting the deuterium lamp signal from the hollow-cathode lamp signal. This method is limited in the spectral range on account of the spectra emittedby a deuterium lamp from 190-400 nm. Background can also be measured by taking readings at a non-absorbing line near the resonance line and then subtracting the results from the measurement at the resonance line. Another method for the correction of background absorption is the Zeeman effect (based on the Zeeman splitting of the absorption line in a magnetic field). This is particularly useful when the background absorption shows fine structure. It permits an efficient background correction in the range of 185-900 nm. CHOICE OF THE OPERATING CONDITIONSAfter selecting the suitable wavelength and slit width for the specific element, the need for the following has to be ascertained:correction for non-specific background absorption,chemical modifiers or ionisation buffers to be added to the sample as well asto blank and reference solutions,dilution of the sample to minimise, for example, physical interferences,details of the temperature programme, preheating, drying, pyrolysis, atomisation, post-atomisation with ramp and hold times,inert gas flow,matrix modifiers for electrothermal atomisation (furnace),chemical reducing reagents for measurements of mercury or other hydride-forming elements along with cold vapour cell or heating cell temperature,specification of furnace design (tank, L vov platform, etc).METHODUse of plastic labware is recommended wherever possible. The preparation of the sample may require a dissolution, a digestion (mostly microwave-assisted), an ignition step or a combination thereof in order to clear up the sample matrix and/or to remove carbon-containing material. If operating in an open system, the ignition temperature should not exceed 600 °C, due to the volatility of some metals, unless otherwise stated in the monograph.Operate an atomic absorption spectrometer in accordance with the manufacturer s instructions at the prescribed wavelength. Introduce a blank solution into the atomic generator and adjust the instrument reading so that it indicates maximum transmission. The blank value may be determined by using solvent to zero the apparatus. Introduce the most concentrated reference solution and adjust the sensitivity to obtain a maximum absorbance reading. Rinse in order to avoid contamination and memory effects. After completing the analysis, rinse with water R or acidified water.If a solid sampling technique is applied, full details of the procedure are provided in the monograph.Ensure that the concentrations to be determined fall preferably within the linear part of the calibration curve. If this is not possible, the calibration plots may also be curved and are then to be applied with appropriate calibration software.Determinations are made by comparison with reference solutions with known concentrations of the element to be determined either by the method of direct calibration (Method I) or the method of standard additions (Method II).METHOD I - DIRECT CALIBRATIONFor routine measurements 3 reference solutions and a blank solution are prepared and examined.Prepare the solution of the substance to be examined (test solution) as prescribed in the monograph. Prepare not fewer than 3 reference solutions ofthe element to be determined, the concentrations of which span the expected value in the test solution. For assay purposes, optimal calibration levels are between 0.7 and 1.3 times the expected content of the element to be determined or the limit prescribed in the monograph. For purity determination, calibration levels are the limit of detection and 1.2 times the limit specified for the element to be determined. Any reagents used in the preparation of the test solution are added to the reference and blank solutions at the same concentration.Introduce each of the solutions into the instrument using the same number of replicates for each of the solutions to obtain a steady reading.Calculation. Prepare a calibration curve from the mean of the readings obtained with the reference solutions by plotting the means as a function of concentration. Determine the concentration of the element in the test solution from the curve obtained.METHOD II - STANDARD ADDITIONSAdd to at least 3 similar volumetric flasks equal volumes of the solution of the substance to be examined (test solution) prepared as prescribed. Add to all but 1 of the flasks progressively larger volumes of a reference solution containing a known concentration of the element to be determined to produce a series of solutions containing steadily increasing concentrations of that element known to give responses in the linear part of the curve, if possible. Dilute the contents of each flask to volume with solvent.Introduce each of the solutions into the instrument, using the same number of replicates for each of the solutions, to obtain a steady reading. Calculation. Calculate the linear equation of the graph using a least-squares fit and derive from it the concentration of the element to be determined in the test solution.VALIDATION OF THE METHODSatisfactory performance of methods prescribed in monographs is verified at suitable time intervals.LINEARITYPrepare and analyse not fewer than 4 reference solutions over the calibration range and a blank solution. Perform not fewer than 5 replicates.The calibration curve is calculated by least-square regression from all measured data. The regression curve, the means, the measured data and the confidence interval of the calibration curve are plotted. The operating method is valid when:the correlation coefficient is at least 0.99,the residuals of each calibration level are randomly distributed around the calibration curve.Calculate the mean and relative standard deviation for the lowest and highest calibration level.When the ratio of the estimated standard deviation of the lowest and the highest calibration level is less than 0.5 or greater than 2.0, a more precise estimation of the calibration curve may be obtained using weighted linear regression. Both linear and quadratic weighting functions are applied to the data to find the most appropriate weighting function to be employed. If the means compared to the calibration curve show a deviation from linearity, two-dimensional linear regression is used.ACCURACYVerify the accuracy preferably by using a certified reference material (CRM). Where this is not possible, perform a test for recovery.Recovery. For assay determinations a recovery of 90 per cent to 110 per cent is to be obtained. For other determinations, for example, for trace element determination the test is not valid if recovery is outside of the range 80 per cent to 120 per cent at the theoretical value. Recovery may be determined on a suitable reference solution (matrix solution) which is spiked with a known quantity of analyte (middle concentration of the calibration range). REPEATABILITYThe repeatability is not greater than 3 per cent for an assay and not greater than 5 per cent for an impurity test.LIMIT OF QUANTIFICATIONVerify that the limit of quantification (for example, determined using the 10 σapproach) is below the value to be measured.。

2A review of research progress on CO capture,storage,and utilization in 34Q156789111213141516171819202122232425262728293031323334353637383940414243444546474849505152535455565758596061626364656667686970717273747576with 58%of the sources being located within the east and south 77central regions.The contributions of large point sources in each 78sector to total CO 2emissions in China are listed in Fig.2[13].With 79rapid development of energy technologies in the 21st century,fos-80sil fuels,especially coal,will still remain the dominant energy0016-2361/$-see front matter Ó2011Elsevier Ltd.All rights reserved.doi:10.1016/j.fuel.2011.08.022⇑Corresponding authors.Q2Address:State Key Laboratory of Coal Conversion,Institute of Coal Chemistry,Chinese Academy of Sciences,Taiyuan 030001,China (Y.Sun).Tel.:+863514049612;fax:+863514041153.E-mail addresses:zhaoning@ (N.Zhao),weiwei@ (W.Wei),yhsun@ (Y.Sun).Please cite this article in press as:L Q1i L et al.A review of research progress on CO 2capture,storage,and utilization in Chinese Academy of Sciences.Fuel(2011),doi:10.1016/j.fuel.2011.08.022source in China for decades to come.Chinese government recognized the huge challenge of CO 2abatement while satisfying ever-increasing energy demand.In the light of this situation,November 26,2009,China officially announced action to control emissions per unit of GDP by 40–45%by 2020,based on 86levels [14].To address this,China is undertaking a range of techni-87cal research and development projects on CCSU,including the na-88tional fundamental research and high-tech programs,as well as a 89large number of international programs.The CCS projects,fun-90dings,and research institutes in China is shown in Table 1.91Since 1990,China had carried out a series of climate change 92projects under framework of national programs,such as China’s 93National Climate Change Program (CNCCP),National Hi-tech R&D949596979899100101102103104105106107108109110111112113114115116117118119120121cooperation with international on CCSU.On the basis of the finical 122support of both Chinese government and CAS,a lot of progresses 123were obtained in several academic institutes in CAS including 124CO 2capture;enhanced oil recovery (EOR)and enhanced coal bed 125methane (ECBM)projects as well as CO 2chemical utilizations.This 126brief review has covered the research progress in CO 2capture,stor-127age,and utilization in CAS.2.The contributions of large point sources in each sector to overall total emissions in China [12].Please cite this article in press as:L Q1i L et al.A review of research progress on CO 2capture,storage,and utilization in Chinese Academy of Sciences.Fuel(2011),doi:10.1016/j.fuel.2011.08.022128129130131132133134135136137aration,and cryogenic fractionation.138 2.1.Amine-based scrubbing solvent139Amine scrubbing is a well known technology for capturing CO 2140from flue gas,which has been widely deployed on a large scale 141across several industries [25–28].The industrially most important142143144145146147148149150151152the environment [30].1532.2.Ionic liquids154Therefore,a nonvolatile solvent that could facilitate CO 2capture 155without the loss of solvent into the gas stream would be advanta-156geous.Ionic liquids (ILs)are commonly defined as liquids whichTable 1CCS projects,fundings,and research institutes in China.China and international cooperation on CCS projects and fundingsResearch institutes aBNLMS–CAS IET–CAS RCEES–CAS ICC–CAS IPE–CAS LICP–CAS CIAC–CAS National High Technology Research and Development Program of China (863)SIC–CAS National Key Basic Research and Development Program of China (973)IGG–CAS China’s National Climate Change Program (CNCCP)IAP–CAS L.L Q1i et al./Fuel xxx (2011)xxx–xxx3Please cite this article in press as:L Q1i L et al.A review of research progress on CO 2capture,storage,and utilization in Chinese Academy of Sciences.Fuel(2011),doi:10.1016/j.fuel.2011.08.022157are composed entirely of ions with a melting point of less than 158100°C.ILs have many unique properties in comparison to other 159solvents as extremely low volatility,broad range of liquid temper-160ature,high thermal and chemical stability,and tunable physico-161chemical characteristics and as a result,ILs have been considered 162as a potential substitute of aqueous amine solutions for CO 2cap-163ture [31–34].164In Changchun Institute of Applied Chemistry,Chinese Academy 165of Sciences (CIAC–CAS),a novel dissolving process for chitin and 166chitosan was developed by using the ionic liquid 1-butyl-3-167methyl-imidazolium chloride ([Bmim]Cl)as a solvent for capturing 168and releasing CO 2.The results showed that the chitin/IL and chito-169170171172173174175176177178179180181182183184185186187188189190191192193194195196197198199200201tant to consider the maximum mass loading when considering the 202support of ILs on inert substrates –yes,these can enhance the ILs’203ability to take up CO 2,but at the expense of cycling an inert sorbent 204round a thermal cycle.The ILs are also monstrously expensive,the 205complex structure,and high cost for preparation,compared to sim-206pler solvents such as MEA or ammonia.Thus,the potential for 207improving CO 2solubilities and reducing cost of the ILs still needs 208to be studied for future applications.In 2010,in Beijing National 209Laboratory for Molecular,Chinese Academy of Sciences (BNLMS–210CAS),Zhang and co-workers first reported on CO 2capture by 211hydrocarbon surfactant liquids.It also found that CO 2had high sol-212ubility in low-cost hydrocarbon surfactant liquids,and the ab-213and the 214215216such as corrosion,at 217regenerable solid sor-218concept for CO 2recov-219into amine-based and 220221222with various so-223as silica gels,activated 224have been shown to phys-225enhance the sorp-226of many amine-based 227In Dalian Institute of 228(DICP–CAS),Zhang 229silica foam (MCF)materi-230with polyethyl-231The results showed that 232having large window 2333.45mmol CO 2/g sorbent 234In Institute of Coal Chem-235Zhao et al.studied 236materials derived 237sorption capabili-238°C and 1bar.The as-pre-239selectivity for CO 2over 240prepared a series of CO 2241pentamine (TEPA)was 242(PMHS)based mesopor-243The highest absorption 24475°C with the 10vol.%245was higher than most 246Desorption could 247in 1h [46].248of amine-based sorbent 249capacity of solid sorbent.250have poor mechanical 251amine-based sorbents 252and require signifi-253processes.254255sorbents for CO 2capture 256Alkali earth metal,such 257form alkali earth metal-258vapor at high tempera-259and post-combus-260simplified process flow 261the calcium looping 262vessel (the carbonator)4L.L Q1i et al./Fuel xxx (2011)xxx–xxxPlease cite this article in press as:L Q1i L et al.A review of research progress on CO 2capture,storage,and utilization in Chinese Academy of Sciences.Fuel(2011),doi:10.1016/j.fuel.2011.08.022the carbonation reaction between CO 2and solid CaO separates CO from coal-combustion flue gas at a temperature between 600°and 650°C.The CaCO 3formed is then passed to another vessel (the calciner),where it is heated to reverse the reaction (900–950°C),releasing the CO 2suitable for sequestration,and regener-ating the CaO-sorbent which is then return to the carbonator.The carbonation process is exothermic,which is matched with the temperature of a steam cycle,allowing recuperation of the heat.In IPE–CAS,the decomposition conditions of CaCO 3particles for CO 2capture in a steam dilution atmosphere (20–100%steam 307308309310311312313314315316317318319320321322323324325326327328329330332333334335336337338339340341342343344345346347348349350351352353354355Fig.3.The process flow diagram of post-combustion capture using the calcium looping cycle [47,48].Please cite this article in press as:L Q1i L et al.A review of research progress on CO 2capture,storage,and utilization in Chinese Academy of Sciences.Fuel(2011),doi:10.1016/j.fuel.2011.08.022strength (998N/cm 2)and exhibited good stability in multiple cy-cles [74,75].Furthermore,the application of a conceptual CO 2cap-ture process using this sorbent was proposed for an existing coal fired power plant [75].However,to optimize CO 2sorption capacity,understand of the interaction between CO 2and the sorbent need to be studied in the further work.Moreover,much work remains before the technology fluidized bed CO 2capture can be commercialized.Simulta-neously,the numerical simulation based on the computational fluid 365dynamics (CFD)method will become a research focus in the future.366 3.CO 2storage367Following the capture and transport process,CO 2can be dis-368posed of in natural sites such as deep geological sequestration,369mineral carbonation,or ocean storage [76].There are three geolog-370ical formations that have also been recognized as major potential 371CO 2sinks:deep saline-filled sedimentary (DSFs),depleted oil 372natural gas reservoirs,and unmineable coal-seams.The geology 373also suggests possibilities for CO 2enhanced oil recovery (CO 374EOR),CO 2enhanced gas recovery (CO 2–EGR)and CO 2enhanced 375coal-bed methane recovery (CO 2–ECBM)projects [12].3763.1.Geological sequestration377Geological storage involves injecting CO 2at depths greater than 3781000m into porous sedimentary formations using technologies 379derived from the oil and gas industry [77].CO 2can be stored in 380supercritical state at depth below 800–1000m,which provides 381the potential for efficient utilization of the space,due to the li-382quid-like density of supercritical CO 2.The point at which CO 2Table 2Performance summary of K-based sorbents capturing CO 2.Material Temperature (°C)CO 2partial pressure (bar)e Total capacity (mmol CO 2/g sorbent)Method f Regenerature temperature (°C)Ref.K 2CO 3/AC a 600.01 1.95TCD g 150[62]K 2CO 3/SiO 2600.010.23TCD g –[62]K 2CO 3/USY 600.010.43TCD g –[62]K 2CO 3/CsNaX 600.01 1.35TCD g –[62]K 2CO 3/Al 2O 3600.01 1.93TCD g 350[62]K 2CO 3/CaO 600.01 1.11TCD g –[62]K 2CO 3/MgO 600.01 2.70TCD g 400[62]K 2CO 3/TiO 2600.01 1.89TCD g 150[62]K 2CO 3/Al 2O 3600.01 1.96TCD g >300[63]Re-KAl(I)30b 600.01 1.86TCD g <200[63]g Fig.5.The schematic diagram of experimental apparatus for the fluidized bed [74,75].6L.L Q1i et al./Fuel xxx (2011)xxx–xxxPlease cite this article in press as:L Q1i L et al.A review of research progress on CO 2capture,storage,and utilization in Chinese Academy of Sciences.Fuel(2011),doi:10.1016/j.fuel.2011.08.022383transforms from critical to supercritical point is 31.1°C and 3847.38MPa [78].CO 2is injected usually in the supercritical form into 385the saline aquifer or depleted oil or gas reservoir.Four major clas-386ses of deep geologic reservoirs present within China have been 387identified and evaluated as candidates for the long-term storage 388of anthropogenic CO 2:deep saline-filled sedimentary (DSFs)for-389mations,depleted gas basins,depleted oil basins with potential 390for CO 2–EOR,and deep unmineable coal seams with potential for 391CO 2–ECBM.Fig.6shows the map of the combined location and ex-392tent of candidate geologic CO 2storage formations in China [13].393Because the CO 2industry is not mature,there are few active CO 2394storage projects which can provide site specific information;hence417China are also potential storage candidates.Recently,other re-418search has also focused on estimating the distance between CO 2419sources and potential sinks.Zheng et al.superimposed the loca-420tions of these 27facilities onto maps of sedimentary basins in each 421of the five regions of China (Huabei,Ordos,Dongbei,Yuwan,and 422Xinjiang).The majority of the candidate CO 2sources are found in 423the Ordos,Huabei and Dongbei regions [85].424The China–UK Near Zero Emissions Coal (NZEC)Initiative exam-425ined options for carbon (CO 2)capture,transport and geological 426storage in China,which was developed under the 2005EU–China 427NZEC Agreement that aims to demonstrate CCS in China and the 428EU [16,86–88].The NZEC Initiative has evaluated the potential to 429430431432433434435436437438439440441442443444445446447448449450451L.L Q1i et al./Fuel xxx (2011)xxx–xxx7Please cite this article in press as:L Q1i L et al.A review of research progress on CO 2capture,storage,and utilization in Chinese Academy of Sciences.Fuel(2011),doi:10.1016/j.fuel.2011.08.022452Kailuan mining area (Hebei Province)and deep saline aquifers in 453the Jiyang Depression (Shandong province)[89,90].The results 454show that the Dagang oilfield is not suitable for large-scale storage,455though could be considered for EOR pilots.The Shengli oilfield was 456considered more promising for storage (472Mt in eight selected 457fields).Storage potential in the Kailuan mining area is 504,000458Mt adsorbed onto the coal and 38,100Mt void storage capacity.459However,the coals have low porosity and permeability that will af-460fect future energy resources [90].The Institute of Geology and Geo-461physics,Chinese Academy of Sciences (IGG–CAS)studied the 462potential for storage in the Jiyang Depression.The results revealed 463that Guantao Formation in the Jiyang Depression has good porosity 464and permeability 465areas was 4662010,in South China 467of Sciences 468storage capacity in 469the Pearl River 470CCS-related 471China [78].There 472saline formations 473tive storage 474including 60Mt in 475large for storaging 476in Guangdong in 477In a word,these 478age of CO 2in deep 479Although this is 480countries,it will 481and there was 482characteristics.483 3.1.2.CO 2–EOR484Although CO 2485oil recovery (EOR)486this process can be 487oil,the cost of CO 2,488the CO 2source [92].489the production of 490be an ideal option 49184commercial or 492tion worldwide [1].493been implemented 494Oil Corporation 495in the Daqing,496ernments of Japan 497out a project to 498plant in China into a 499duced from the 500that between 270501ered by using CO 2502including IGG–CAS 503three large oil fields 504oil reservoirs in the 505were suitable both 506found suitable for 507showed that the 508CO 2storage 509the oil recovery by steam injection has been already applied at Lia-510ohe oil field.Each single well,in average,had conducted 7.6times 511of steam injection-oil recovery processing for EOR propose.The to-512tal recovered oil amounts were 12.06Mt [92].Active oil producing 513fields where CO 2–EOR is technically possible provide credible 514opportunities to initiate CO 2storage demonstration projects.How-515ever,significant further investigations,including detailed site516appraisals would be necessary before such fields can be considered 517as technically and economically suitable for CO 2storage.5183.1.3.CO 2–ECBM519In a similar manner,ECBM recovery can be used to store CO 2520while improving methane recovery.A bright prospect of gas injec-521tion technology for ECBM production has been suggested by Chi-522nese engineers since the late 1990s [94].More recently,a joint 523venture was formed between the China United Coal Bed Methane 524Corporation and the Alberta Research Council of Canada to develop 525a project entitled ‘‘Development of China’s coalbed methane tech-526nology/CO 2sequestration’’[12].This project was initiated in March 527project was performed 528in the anthracitic coals of 529China [95],which is 530in China up to now 531at ICC–CAS in 2005532were investigated based 533An equipment simulated 534middle pressures was 535in coal seam,536behaviors were studied.537coal mine and salt-water 538four coals of various rank 539China were tested for 540one of the most impor-541process.The result 542capacities for methane 543>Bulianta coal >Zhangji 544adsorption isotherms 545lattice model [100].546given to estimate the 547[101],which was 548underground stress is so 5492and CH 4respectively 550the mechanical sta-551of the impact factors of 552stress could be obviously 553of the casing or by using 554and Young’s modulus 555China was also estimated 556prospecting data of coal 557and the replacement ratio 558different ranks,it is esti-559methane resources will 560technology is uti-561in coalbeds is about 562as the total CO 2emission 563also developed 564simulation of the CO 2–565is a lack of knowledge 566due to the complexity 567fluid transport processes.568will be the next 569570571Large amounts of CO 2can also be fixed by a process called min-572eral carbonation,which is natural or artificial fixation of CO 2into 573carbonates.It has been proposed as a promising CO 2sequestration 574technology e.g.the silicate rocks (calcium or magnesium)could be 575turned into carbonates by reacting with CO 2following this mech-576anism [8,105]:577ðMg ;Ca Þx Si y O x þ2y þx CO 2!x ðMg ;Ca ÞCO 3þy SiO 25798L.L Q1i et al./Fuel xxx (2011)xxx–xxxPlease cite this article in press as:L Q1i L et al.A review of research progress on CO 2capture,storage,and utilization in Chinese Academy of Sciences.Fuel(2011),doi:10.1016/j.fuel.2011.08.022580581582583584585586587588589590591592593594595596597598599600601602603604605606607608609610611612613614615616617618619620621622623624625626627628629630631632633634635636637638639hanced by the fact that this method of storage is highly verifiable 640and unquestionably permanent,the grinding energy required to 641produce particles of the size required to react rapidly with the 642acids is large,and the residence times on the order of hours re-643quired to allow carbonation of the solids,via either route,is so long 644that immense reactors would be required,associating environmen-645tal concerns.Furthermore,mineral carbonation will always be646expensive than most applications of geological storage 647important gap in mineral carbonation is the lack of 648onstration plant.649Ocean storage650Captured CO 2also could help reduce the atmospheric 6516526536546556566576586596606616626636646656666676686696706716726736746756766776786796806816826836842685carbonic acid,which would be likely harmful to ocean organisms 686and ecosystems [17].Additionally,it is not known whether the 687public will accept the deliberate storage of CO 2in the ocean as part 688of a climate change mitigation strategy.The development of ocean 689storage technology is generally at a conceptual stage;thus,further 690research and development would be needed to make technologies 691available.3.Reaction mechanism for enhanced carbonation crystallization Q1Please cite this article in press as:L Q1i L et al.A review of research progress on CO 2capture,storage,and utilization in Chinese Academy of Sciences.Fuel(2011),doi:10.1016/j.fuel.2011.08.022692693694695696697698699700701702703704705706707708709710711712713714715716717718719721722723the reaction [131–135],such as in ICC–CAS,Zhao et al.had reported 724a catalyst system composed of KI supported on metal oxides for 725cycloaddition of propylene oxide with CO 2.It was found that the 726activity of KI for cycloaddition was greatly enhanced by ZnO as both 727support and promoter,resulting in a high yield of propylene 728carbonate within a short reaction time.The mechanism is also pro-729posed (Scheme 4)[133].Recently,a large number of catalytic730systems,such as metal oxides,transition metal,ammonium 731well as main group complexes,were reported to be active 732reactions [136–139].In ICC–CAS,the efficient ultrasonic tech-733nique was used for the preparation of amine-functionalized porous 734catalysts for CO 2coupling with epoxide.According to 735study by Zhang and co-workers [140],the reaction conditions 736great influence on the performance and the silanols on the surface 737played an important role in the chemical fixation of CO 2.In addi-738they also proposed the possible reaction mechanism for 739coupling with epoxide over such type of catalysts (Scheme 5).740In recent years,ionic liquids as environmentally benign media 741organic synthesis and catalytic reaction significant progress 7427437447457467477487492750catalyst system without using additional organic solvents was 751achieved in excellent selectivity and TOF (5410h À1)[144].In 752IPE–CAS,an efficient Lewis acid/base catalyst composed of ZnCl 2/753PPh 3C 6H 13Br was developed and showed high activity and selectiv-754ity for the coupling reaction of CO 2and epoxide under the mild 755conditions [145].Sun et al.prepared a series of hydroxyl-function-756alized ionic liquids (HFILs)which showed efficient reactivity andScheme 4.The proposed diagram of reaction mechanism [133].Q1Please cite this article in press as:L Q1i L et al.A review of research progress on CO 2capture,storage,and utilization in Chinese Academy of Sciences.Fuel(2011),doi:10.1016/j.fuel.2011.08.022780781782783784785786787788789790791792793794795796797798799800802803804805806807Please cite this article in press as:L Q1i L et al.A review of research progress on CO 2capture,storage,and utilization in Chinese Academy of Sciences.Fuel(2011),doi:10.1016/j.fuel.2011.08.022CO 2þCH 4¼2CO þ2H 2841842In the past decade,a lot of researches have been devoted to the 843catalytic performance of noble metals,including Pt,Ru,Rh,Pd,844and Ir for this reaction [165–169].It showed that Rh and Ru845exhibited both high activity and stability in CH 4dry reforming,846while Pd,Pt and Ir were less active and prone to deactivation.847Nevertheless,considering the aspects of high cost and limitedPlease cite this article in press as:L Q1i L et al.A review of research progress on CO 2capture,storage,and utilization in Chinese Academy of Sciences.Fuel(2011),doi:10.1016/j.fuel.2011.08.022848availability of noble metals,it is more practical to develop non-849noble metal catalysts which exhibited both high activity and pared with noble metals,Ni-based catalysts have been 851widely investigated because of their high activity and relatively 852low price [170–172].Nevertheless,application of Ni-based cata-853lysts in a large scale process is not so straightforward due to rapid 854carbon deposition,resulting in the deactivation of the catalyst 855[173].It was found that when Ni is supported on a alkaline earth 856metal oxide such as MgO,CaO,and BaO with strong Lewis basi-857city,carbon deposition can be attenuated or even suppressed 858[174]which is because that the support could promote chemi-859sorption of CO 2and thus,accelerated the reaction of CO 2and C 8608618628638648658668678688698708718728738748758768778788798808818828838848858868878888898908918928938948958968974.4.Reaction of CO 2with ethane and propane898Ethylene and propylene are basic raw material in the petrol-899chemical industry.Thermal cracking of hydrocarbons (such as eth-900ane)in the presence of steam is currently the main source of eth-901ylene [181,182].Nevertheless,steam cracking of ethane to 902ethylene is a highly endothermic process that must be performed 903at high temperatures,which means the consumption of a large 904amount of energy.The introduction of CO 2could reduce the extent 905of deep oxidation which results in many byproducts whereas eth-906ylene selectivity drops when oxygen is used as oxidant [183].907Thermodynamics analysis and experimental results have indi-908909910911912913915916917918919920921922923924925926927928929930931932933934935936938939940941L.L Q1i et al./Fuel xxx (2011)xxx–xxx13Please cite this article in press as:L Q1i L et al.A review of research progress on CO 2capture,storage,and utilization in Chinese Academy of Sciences.Fuel(2011),doi:10.1016/j.fuel.2011.08.022969970971972973974975976977978979980981982983984985986987988990991992993994995996997998999100010011002100310041005100610071008100910101011101210131014Please cite this article in press as:L Q1i L et al.A review of research progress on CO 2capture,storage,and utilization in Chinese Academy of Sciences.Fuel(2011),doi:10.1016/j.fuel.2011.08.0221015DMC in supercritical phase was proposed in Scheme 11.Recently,developed a supported Cu-Ni/V 2O 5-SiO 2heterogeneous because the reaction can be carried out in a fixed-bed the side production of water molecules 10341035103610371038103910401041104210431044and theoretical approaches,which enable the development of 1045CO 2selective sorbents.Besides,the sorbent performance,lifetime,10461047104810491050105110521053105410551056105710581059106010611062106310641065Scheme 11.The proposed catalytic reaction mechanism Please cite this article in press as:L Q1i L et al.A review of research progress on CO 2capture,storage,and utilization in Chinese Academy of Sciences.Fuel(2011),doi:10.1016/j.fuel.2011.08.0221066of component costs,specific Chinese market conditions,and other 1067factors impacting costs of deployment in China will be important 1068to consider in greater detail.To propose the storage mechanism,1069monitoring,simulation,risk assessment,control methods as well 1070as engineering design will be studied in future.1071The utilization of CO 2to chemicals has attracted considerable 1072attention as a possible way to manufacture useful commercial 1073chemicals from CO 2in some specific locations (Scheme 12)[222].1074The utilization of CO 2as a raw material in the synthesis of chemi-1075cals was also conducted by CAS,including synthesis of cyclic car-1076bonate from CO 2and epoxide,reaction of CO 2and propylene 1077glycol (PG),CO 2reforming of CH 4,reaction of CO 2and ethane 1078and propane,CO 21079methyl carbonate 1080amount of CO 2can 1081to the order of 1082ent the typical 1083cations is only 1084laminates are used 1085of the materials can 1086and overall net 1087ation.1088and fundamental 1089lue-added chemicals 1090tive net carbon 1091moderate reaction 1092the energy or 1093clear,wind,1094also important to 1095 6.Uncited 1096[201].Q31097Acknowledgments1098This work was 1099vation Programme 1100323);the Ministry of 1101lic of China 1102Climate Change:1103Academy of 1104the 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第20卷第8期装备环境工程2023年8月EQUIPMENT ENVIRONMENTAL ENGINEERING·45·高强不锈钢在海水环境中的阴极保护行为研究王鑫，白双锋，郭云峰，黄哲华，李相波，侯健，张慧霞 （中国船舶集团有限公司第七二五研究所 海洋腐蚀与防护重点实验室，山东 青岛 266237）摘要：目的研究不同阴极极化电位下高强不锈钢的极化行为，确定某高强不锈钢合理的阴极保护电位区间。

方法通过动电位极化测试以及电化学阻抗测试等电化学测试手段，研究此种高强不锈钢在海水中的阴极反应过程，通过不同极化电位下的恒电位极化测试，结合扫描电子显微镜和能谱仪，观察分析试样表面的腐蚀产物，研究阴极极化电位对高强不锈钢表面阴极产物膜的影响规律，以及对高强不锈钢在海水中的阴极保护效果。

结果动电位极化测试表明，在‒0.50~‒0.90 V，只需要施加很小的阴极电流，就可使极化电位发生显著变化。

电化学阻抗谱测试及拟合结果表明，极化电位在‒0.70 V时，电极反应的电荷转移电阻最大，此时腐蚀被完全抑制。

恒电位极化测试发现，随着电位负移，极化电流密度整体上呈现先减小、后增大的趋势。

用能谱仪分析其表面产物发现，钙镁沉积层的致密度呈现先增加、后降低的趋势。

结论此种高强不锈钢在海水环境中施加阴极电位为‒0.50~‒1.00 V时，可以得到有效保护。

关键词：海洋工程；高强不锈钢；阴极保护；阴极极化；电化学行为；XRD中图分类号：TG174.41 文献标识码：A 文章编号：1672-9242(2023)08-0045-08DOI：10.7643/ issn.1672-9242.2023.08.007Cathodic Protection Behaviors of High Strength Stainless Steel in Seawater WANG Xin1, BAI Shuang-feng1, GUO Yun-feng1, HUANG Zhe-hua1, LI Xiang-bo1, HOU Jian1, ZHANG Hui-xia1(State Key Laboratory for Marine Corrosion and Protection, Luoyang Ship Material ResearchInstitute, Shandong Qingdao 266237, China)ABSTRACT: The work aims to study the polarization behavior of high strength stainless steel at different cathodic polarization potentials, so as to determine the reasonable cathodic protection potential range of high strength stainless steel. The cathodic re-action process of the high strength stainless steel was studied by electrochemical test methods such as potentiodynamic polariza-tion test and electrochemical impedance test. The corrosion products on the surface of the samples were observed and analyzed by cathodic polarization combined with scanning electron microscope and energy dispersive spectrometer. The effect of ca-thodic polarization potential on the cathodic product film on the surface of the high strength stainless steel and the cathodic pro-tection effect of the high strength stainless steel in seawater were studied. Potentiodynamic polarization test indicated that when the cathode polarization potential was ‒0.50 V~‒0.9 V, only a small cathode current could make the polarization potential change significantly. Electrochemical impedance spectroscopy test and fitting results show that when the polarization potential收稿日期：2023-04-03；修订日期：2023-06-15Received：2023-04-03；Revised：2023-06-15作者简介：王鑫（1996—），女，硕士。

[American Journal of Science,Vol.304,December,2004,P.839–861] American Journal of ScienceDECEMBER2004THE EVOLUTION OF THE EARTH SURFACE SULFUR RESERVOIRD.E.CANFIELDDanish Center for Earth System Science(DCESS)and Institute of Biology,University of Southern Denmark,Campusvej55,5230Odense M,Denmark;e-mail:dec@biology.sdu.dkABSTRACT.The surface sulfur reservoir is in intimate contact with the mantle. Over long time scales,exchange with the mantle has influenced the surface reservoir size and possibly its isotopic composition.Processes delivering sulfur to the Earth surface from the mantle include volcanic outgassing,hydrothermal input,and ocean crust weathering.The sulfidefixed in ocean crust as a consequence of hydrothermal sulfate reduction,and subduction of sedimentary sulfides,represent return pathways of sulfur to the mantle.The importance of these different pathways in influencing the size of the surface sulfur reservoir depends on the particulars of ocean and atmo-sphere chemistry.During times of banded iron formation when the oceans contained dissolved iron,sulfide from submarine hydrothermal activity was precipitated on the seafloor and subsequently subducted back into the mantle and,therefore,had little impact on the surface sulfur reservoir size.With sulfidic ocean bottom water condi-tions,which may have occurred through long stretches of the Mesoproterozoic and Neoproterozoic,significant amounts of sulfide is subducted into the mantle.When the oceans are oxic,sulfide subduction is unimportant,and an additional source,ocean crust weathering,delivers sulfur to the Earth surface.Thus,under oxic conditions the surface environment accumulates sulfur,and probably has for most of the last700 million years.Mass balance modeling suggests that the surface sulfur reservoir may have peaked in size in the early Mesoproterozoic,declined to a minimum in the Neoproterozoic, and increased to its present size through the Phanerozoic.The exchange of sulfur between the mantle and the surface environment can also influence the isotopic composition of the surface reservoir.Modeling shows that the subduction of34S-depleted sulfur through the Mesoproterzoic could have significantly increased the average␦34S of the surface reservoir into the late Neoproterozoic.The preserved isotope record through the Neoproterozoic is well out of balance,with the average ␦34S for sulfate and sulfide both exceeding the modern crustal average.This imbal-ance could be explained,at least partly,if the crustal average was more34S-enriched than at present,as the modeling presented here suggests.introductionSulfur is an essential ingredient of life,and in oxidation states ranging fromϪ2to ϩ6,it fuels the metabolism of countless different prokaryotic organisms,some of which evolved early in the history of life on Earth(Canfield and Raiswell,1999). Microbial metabolism via sulfate reduction is of particular importance,contributing to around1⁄2of the carbon remineralization in coastal marine sediments(Jørgensen, 1982;Canfield,1993).Pyrite(FeS2)is an ultimate product of sulfate reduction,and its burial in sediments,and weathering on land,significantly influence the oxygen balance of the atmosphere(Garrels and Perry,1974;Berner and others,2000).The availability of sulfur to organisms and the magnitude of sulfur redox cycling will depend on the amount of sulfur available at the Earth surface and its oxidation state. This in turn should depend on the balance of sulfur exchange processes between the839840 D.E.Canfield—The evolution of the Earth surfaceEarth surface and the mantle.This balance,as will be explored in more detail below, depends on the details of ocean and atmosphere chemistry as they control the routes and the degree to which sulfur is exchanged between the mantle and the surface reservoir.Additionally,the isotopic composition of the whole surface reservoir can be affected if sulfur is exchanged with the mantle with an isotopic composition different from the average crustal reservoir.The reservoir exchange aspect of sulfur dynamics was explored by Hansen and Wallmann(2003)over the last145million years and is explored over much longer time scales here.The purpose of the present contribution is to explore the long term evolution of the sulfur cycle over geologic time.Also explored are the isotopic consequences of this cycling,with an emphasis on the Neoproterozoic sulfur cycle which appears to be isotopically out of balance.the sulfur cycleSulfur,in its principal forms as either pyrite(FeS2)or gypsum(CaSO4⅐2H2O) (with minor organic sulfur),is weathered from the continents as sulfate(SO42Ϫ),and delivered to the oceans(fig.1).Here,bacterial sulfate reduction reduces sulfate to sulfide,which can precipitate as pyrite in sediments,while seawater sulfate can also evaporatively precipitate as gypsum in isolated basins(Garrels and Perry,1974;Berner and Raiswell,1983).Over time these sulfur deposits become uplifted and exposed to weathering.The surface reservoirs are also connected to the mantle(Holser and others,1988;Alt and others,1989;Hansen and Wallmann,2003),and three principal types of mantle sulfur input can be recognized(fig.1).First,SO2,with subordinate H2S,outgasses from terrestrial volcanoes,mostly in convergent plate margins(Stoiber and others,1987;Holser and others,1988;Schlesinger,1997;Halmer and others, 2002),but also from hot spot volcanics.This sulfur source is primarily of mantle origin (Sakai and others,1982;de Hoog and others,2001).However,the isotopic composi-tion of basalts and associated gases from convergent margins can be quite enriched in ␦34S compared to the mantle(Kasasaku and others,1999;de Hoog and others,2001), implying a contribution also from sulfate in subducted marine sediment pore waters (de Hoog and others,2001).Some subducted sedimentary pyrite might also contrib-ute to the volcanic gas,but its contribution is minor compared to sulfate given the generally enriched␦34S values of the volcanic gas.Estimates of the magnitude of this flux vary widely from low values of around1ϫ1011mol yrϪ1to high values of14molϫ1011mol yrϪ1(Stoiber and others,1987;Holser and others,1988;Schlesinger,1997; Halmer and others,2002).Most estimates tend towards the lower end of this range, with values most likely between about1to3ϫ1011mol yrϪ1of primary mantle sulfur (table1).Sulfide also vents to seawater as a result of subaqueous volcanism associated with ocean spreading centers(Von Damm,1990;Elderfield and Schultz,1996).The sulfur is released from hydrothermalfluids circulating through the volcanic system,and no more than30percent of this sulfur originates from seawater sulfate during hydrother-mal circulation.The rest is from the mantle(Shanks and Seyfried,1987;Von Damm, 1990).Estimates of thisflux are obtained by combining ventfluid sulfide concentra-tion with estimates of the waterflux through the high temperature vents.Measured sulfide concentrations vary widely,and estimates of the magnitude of the sulfideflux range from0.9to9.6ϫ1011mol yrϪ1(Elderfield and Schultz,1996).Alternatively,estimates of sulfur exchange rates with the ocean crust are obtained from mass balance calculations on the isotopic compositions and concentrations of sulfur in sections of altered crust.Altered sections of crust show an upper region of sulfide removal.Some of the sulfur is lost during degassing of the basalts during crystallization and some by oxidative weathering of the volcanic rocks(Alt,1994;Bach and Edwards,2003).A lower zone of sulfide dissolution is also found within thesheeted dike complex and the upper gabbro zone (Alt and others,1989,1995;Alt,1994).In addition,there is a pronounced zone of secondary sulfide precipitation in the transition zone between the upper volcanic rocks and the sheeted dikes below.Some of this sulfur comes from sulfide released from the sheeted dikes,and some comes from the reduction of seawater sulfate deeper in the crust at high temperatures.In total,the dissolution and oxidation of ocean crust sulfides contributes about 0.8ϫ1011mol y Ϫ1of sulfur to the oceans.This estimate is based on mass balance calculations of the Troodos ophiolite (Alt,1994)and altered ocean crust off the Costa Rican coast (DSDP site 504B;Alt and others,1989).A similar estimate of 1.1Ϯ0.7ϫ1011mol y Ϫ1is provided by Bach and Edwards (2003).Of this total sulfur input,about equal amounts come from the upper pillow basalts and from the lower sheeted dikes and upper gabbros.Within the upper basalts,about 1⁄2of the sulfur is lost,probably,from degassing during crystallization,and about 1⁄2from oxidative weathering.The sulfur input flux calculated from crustal mass balance is at the lower end of the range determined from vent fluid chemistry.Thereduction Fig.1.A simplified version of the sulfur cycle is shown.The ocean (O)(also including the atmosphere)is the conduit through which sulfur transits.The sulfide reservoir (Sd)includes all sedimentary sulfides;both recently deposited and ancient,while the sulfate reservoir (St)includes seawater sulfate and sulfate evaporites.Both sulfate and sulfide are buried (b)from the ocean into the sulfide and sulfate reservoirs,which are subsequently uplifted onto land and exposed to chemical weathering (w),returning sulfur back to the oceans as sulfate.The boxes representing the ocean (O),sulfide (Sd),and sulfate (St)are the surficial reservoirs of sulfur.The surficial reservoirs are connected to the mantle (M)from which sulfur escapes by volcanic outgassing (vo),hydrothermal circulation through ocean spreading centers (hy),and the oxidative weathering of ocean crust (ocw)during off axis lower temperature hydrothermal circulation.Sulfur is returned to the mantle by the subduction of sedimentary sulfides formed during times of ocean anoxia (see text).Sulfides are also formed and fixed within the ocean crust during high temperature hydrothermal circulation where sulfate is inorganically reduced to sulfide.This transit path is shown from the sulfate box (St)into the mantle (M).841sulfur reservoirof seawater sulfate during hydrothermal circulation and its precipitation in altered ocean crust is a sulfur sink into the mantle and will be considered in more detail below.Sulfate is removed as anhydrite into ocean crust during high temperature hydro-thermal circulation of seawater at ocean spreading centers (Alt and others,1989).Most of the anhydrite is redissolved and returned to the ocean during lower temperature,off-axis circulation (Alt and others,1989;Alt,1994).As noted above,a small portion of the circulating sulfate is,however,reduced to sulfide,and some of this is fixed as solid phase sulfide minerals,forming a return path of sulfur back into the mantle (Alt and others,1989).From the analysis of the sulfur and Fe chemistry of ocean basalts of a variety of ages Bach and Edwards (2003)conclude that Fe and sulfide in the upper pillow lavas might be more extensively oxidized than envisaged by Alt and others (1989).However,whether this oxidation influences the sulfide reduced during high temperature hydrothermal sulfate reduction is unclear.From Alt (1994)the rates of sulfide retention as a result of high temperature sulfate reduction are estimated at about 0.9ϫ1011mol y Ϫ1for the Troodos ophiolite,and 0.4ϫ1011mol yr Ϫ1for the DSDP hole 504B,and these estimates will be used here.There is,in addition,the uptake of metal sulfides associated with microbial and thermochemical sulfate reduction in serpentinized ocean crust (Alt and Shanks,1998),as well as some anhydrite precipitation.The magnitude of this flux is poorly constrained and probably lies somewhere between 0.13to 1.9ϫ1011mol yr Ϫ1(Alt and Shanks,2003).Hence,it could be an important return route of sulfur back into the mantle.However,the modeling from Hansen and Wallmann (2003)suggests that the flux probably lies towards the lower end of the estimates,and in the modeling that follows sulfur removal associated with serpentinization will not be considered.The subduction of pyritized marine sediments constitutes another potential return pathway for sulfur into the mantle.Most deep-sea sediments entering subduc-tion zones are subducted into the mantle at an estimated Cenozoic average of 1.0km 3y Ϫ1(von Huene and Scholl,1991).Subduction erosion also removes crustal material into the mantle.During subduction erosion material from the upper overriding plate is eroded and entrained by the subducting slab (von Huene and Scholl,1991).The material removed by subduction erosion is a complex mix of accreted sediment (in accretionary prisms)and crystalline rock.Overall,subduction erosion removes about 1.5km 3y Ϫ1of material into the mantle (von Huene and Scholl,1991).Table 1Magnitude of present-day fluxes into and out of themantle.asee fig.1for key to letter designations.b not including ocean crust weathering which is listed separately.c potential rate when the oceans are sulfidic.1,Stoiber and others (1987);2,Holser and others (1988);3,Elderfield and Schultz (1996);4,Alt (1994);5,Alt and others (1989).842 D.E.Canfield—The evolution of the Earth surfaceAs deep-sea sediments generally contain little pyrite today,the subduction of deep-sea sediments presently removes little pyrite into the mantle.There are no estimates of the pyrite content of material removed into the mantle by subduction erosion.However,crystalline crustal rock is likely to be pyrite poor,and much of the accreted sediment removed by subduction erosion is likely derived from the deep sea,which is also presently pyrite poor.Thus,overall,subduction is probably not today an important removal pathway of pyrite into the mantle.However,this would change during times of sulfidic ocean bottom water conditions as probably occurred during a substantial portion of the middle Proterozoic (Canfield,1998;Shen and others,2002,2003;Arnold and others,2004;Poulton and others,2004),and also during isolated times in the Phanerozoic (Berry and Wilde,1978).The magnitude of this sink is calculated from the subduction rate of terrigenous sediments into the mantle,esti-mated at between 1ϫ1015to 2.5x1015g yr Ϫ1(Hay and others,1988;von Huene and Scholl,1991).This sediment is assumed to have a total Fe content of 4weight percent,and furthermore,about 25percent of this Fe is assumed to be reactive toward sulfide,as is true for modern deep-sea sediments (Raiswell and Canfield,1998).With these figures,a removal rate of total sulfide,as pyrite,into the mantle of between 3.6ϫ1011to 9ϫ1011moles yr Ϫ1is obtained (table 1).This range of estimates could be viewed as a maximum removal rate of pyrite assuming the whole ocean deep-ocean floor is exposed to sulfide.sulfur cycle over geologic timeIn what follows,the evolution of the sulfur cycle will be considered from two different perspectives.Considered first is the isotope record of sulfide and sulfate over geologic time.From this record we can explore the relative burial histories of sulfate and sulfide as they pertain to the evolution of the oxidation state of the sulfur reservoir through time.A model reconstructing the size of the surface sulfur reservoir provides the second perspective of the evolution of sulfur cycle.Here,the processes controlling the inputs and outputs to the surface reservoir depend on the oxidation state of the atmosphere and oceans.It is shown that the size of the surface reservoir has been dynamic through Earth history.These perspectives combine when considering the isotope record in more detail,where important episodes of apparent isotope imbal-ance are found.This imbalance can be evaluated,at least in part,from the growth history of the sulfur reservoir as deduced from the model results.The Isotope Record of Sulfur Cycle EvolutionThe history of sulfide and sulfate removal from the oceans can be determined from the isotope record of sedimentary sulfides and seawater sulfate (Holland,1973;Garrels and Lerman,1981)using the following mass balance expression:f py ϭ͑␦34S in Ϫ␦34S sul ͒/͑␦34S py Ϫ␦34S sul ͒,(1)where f py is the fraction of total sulfur removed from the oceans as pyrite (the remainder is as sulfate),␦34S in is the isotopic composition of sulfur weathered from the continents and delivered to the oceans,␦34S sul is the isotopic composition of seawater sulfate,and ␦34S py is the average isotopic composition of pyrite sulfur removed from the oceans.Over 3000analyses of the isotopic composition of sedimentary pyrites through time have been compiled (Canfield,1998,2001)and these are calculated into averages for individual geological formations and further averaged over specific time periods.Through the Phanerozoic,averages have been calculated over individual geological periods,and three time slices of 0.54to 0.6Ga,0.6to 0.7Ga,and 0.7to 1.0Ga were used for the Neoproterozoic.Through the remainder of the Precambrian,300million 843sulfur reservoir844 D.E.Canfield—The evolution of the Earth surfaceyear time slices have been used.The average isotopic compositions of individualgeologic formations,and for specific time periods,are shown infiingperiod averages,and the isotopic composition of seawater sulfate through time(whichis not well constrained through broad periods of the Precambrian;Strauss,1993;Canfield,1998,but as we shall see below,this uncertainty matters very little incalculating f py in the Precambrian)(fig.2A),f py is calculated for the last2.75Gaassuming a constant␦34S in of3permil(Holser and others,1988).It is likely that␦34S inhas varied through time,and this will be fully explored in a latter section.Before2.75Ga,small and uncertain differences between␦34S py,␦34S in,and␦34S sul,yield unreliable results,and these calculations have been abandoned.Uncertainty in the calculation off py reflects the standard deviations obtained from averaging together individualformation averages within specific time periods.From these compilations a few general,but important,observations can be made.First,from the Archean through the Mesoproterozoic the average isotopic composi-tion of sulfide straddles the present-day input␦34S of3permil plus or minus about3permil(fig.2A).During the Neoproterozoic,the average isotopic composition ofsulfide increases dramatically and approaches the isotopic composition of sulfate.Theaverage isotopic composition of sulfide drops sharply into the Phanerozoic,withdecidedly negative␦34S values by the Mesozoic.As expected,when the isotopic composition of sulfide is near the isotopiccomposition of sulfate input to the oceans(␦34S pyϷ␦34S in),pyrite burial is the dominant sulfur removal pathway.This follows directly from equation(1).Also from equation(1),when␦34S pyϷ␦34S in the isotopic composition of sulfate has little influence on the calculation of f py.Overall,through the late Archean,the Paleopro-terozoic,and the whole of the Mesoproterozoic,the isotope record is consistent with dominant pyrite removal from the oceans with little evidence for significant sulfate precipitation.Consistent with this,evidence for large sulfate deposits is generally absent in the Archean and in the early Proterozoic,and there are only a few Mesoproterozoic sulfate deposits of note(Grotzinger and Kasting,1993)with sizes ranging from109to1010m3.Although these deposits seem large,their size can only account for10to100years of sulfate input to the oceans at the present rate of2ϫ1012 mol yrϪ1(Berner and Berner,1996).They,therefore,represent only small amounts of sulfur removal.Some sulfate deposits have undoubtedly long since weathered away, but one can only speculate as to the magnitude of such deposits.By about0.8Ga sulfate deposition becomes more pronounced,and some signifi-cant massive sulfate deposits are found,like those from the Amadeus Basin,northern Australia(Grotzinger and Kasting,1993;Gorjan and others,2000)and the Little Dal Group from the Mackenzie Mountains Supergroup of Canada,as well as the0.75Ga Shaler Group on Victoria Island,Canada.Despite this,sulfate deposition is not indicated infigure2B.Indeed,during most of the Neoproterozoic,the calculation of f py reveals impossibly high pyrite burial proportions(fig.4A;see also Hayes and others, 1992;Gorjan and others,2000).The nature of these high f py values and the Neoprotero-zoic sulfur cycle in general will be considered in more detail in a later section.It appears from the isotope record that significant deposition of sulfate from the oceans is mainly a phenomenon of the Phanerozoic(last0.54Ga)and particularly the last0.3Ga(fig.2B).Increased deposition of sulfate would logically reflect increased levels of atmospheric oxygen in the late Precambrian(Berkner and Marshall,1965; Knoll,1992;Canfield and Teske,1996)and more effective oxidation of surficial pyrite to sulfate,increasing the levels of sulfate in the ocean.Probably also contributory is the switch from sulfidic to oxic bottom waters(see below)reducting in the size of the sulfide sink and the magnitude of pyrite burial.Summarizing these points:Fig.2.(A)The isotopic composition of sedimentary sulfides is shown,averaged into formation averages,and period averages.Through the Phanerozoic,period averages represent the geologic periods.In the Neoproterozoic period averages represent the intervals 0.54to 0.6Ga,0.6to 0.7Ga,and 0.7to 1.0Ga.Through the remainder of the Precambrian period averages were compiled for every 0.3Ga.Also shown is the isotopic composition of seawater sulfate through time.Data are from Canfield (2001).(B)The fraction of total sulfur buried as pyrite is presented.This fraction is calculated from period averages utilizing equation (1).The error bars represent the standard deviation from period averages.Note that for the time interval 0.6to 0.7Ga the fraction pyrite burial (equal to 4.4)is off scale with only the bottom of the error bar showing.845sulfur reservoir846 D.E.Canfield—The evolution of the Earth surface1)There is little evidence for significant sulfate deposition in the Archean,Paleoproterozoic,and Mesoproterozoic,consistent with low levels of seawater sulfate at this time.2)The sulfur cycle in the Neoproterozoic is apparently out of balance isotopi-cally.A great deal of34S-depleted sulfide is missing from the record.3)Thefirst indication of significant sulfate precipitation is in the Phanerozoic inresponse to increasing atmospheric oxygen and subsequent increases in seawater sulfate concentrations,as well as a reduction in the extent of sulfidic ocean bottom water.Evolution of the Earth-surface Sulfur ReservoirThe inventory of sulfur at the Earth surface includes sulfate in the oceans,as well as sulfate and sulfide in contemporary sediments and in sedimentary rocks preserved on the continents and in epicontinental settings.This inventory is controlled by the balance of sulfurfluxes into and out of the mantle.As proposed here,thesefluxes have varied in intensity and direction in response to changes in ocean and atmospheric chemistry through time.In what follows,the history of ocean and atmosphere chemistry will be reviewed,and its influence on sulfurfluxes into and out of the mantle will be highlighted.The substantial deposition of banded iron formations(BIFs)in the Archean and early Proterozoic indicates prolonged periods of deep iron-containing ocean water (for example,Holland,1984)from which hydrothermally-derived sulfides would be immediately precipitated as iron sulfide minerals on the oceanfloor.Most of this sulfide would be delivered back with the subduction of deep-ocean sediments and would have contributed little to the growth of the Earth surface sulfur reservoir. Atmospheric oxygen was also low(for example,Holland,1994;Farquhar and others, 2000),and the deep ocean was anoxic,so no seafloor weathering of sulfide minerals was possible.Therefore,the only significant source of sulfur to the early Earth surface was the direct volcanic outgassing of SO2and H2S to the atmosphere and surface waters.Seawater sulfate concentrations were also low,below200␮M before about2.4 Ga,and probably around1mM into the early Proterozoic(Habicht and others,2002; Shen and others,2002).Thus,the high temperature reduction of seawater sulfate at ocean spreading centers was not important.Persistent BIF formation occurred before 2.4Ga and between about1.8Ga and2.0(Isley and Abbott,1999).There is no indication for significant BIF deposition between2.0and2.4Ga.The nature of deep-water chemistry during this time is therefore uncertain.Deep waters may have contained Fe,with the evidence thus far elusive,or they may have contained sulfide as suggested by Bjerrum and Canfield(2002).Alternatively,they may have been oxic.In what follows an Fe-containing bottom water is assumed,with the recognition that modeling should be revised as more information on early Proterozoic bottom water chemistry becomes available.A cartoon of the sulfur cycle prior to1.8Ga is shown infigure3A.Increasing ocean sulfate concentrations through the early Proterozoic toϾ1mM likely favored increasing rates of sulfide production by sulfate reduction,overwhelm-ing iron delivery rates to the oceans by1.8Ga and causing the transition from iron-rich to sulfide-rich deep ocean water(Canfield,1998).This condition may have lasted until late in the Neoproterozoic.Some accumulating observational data support this hypoth-esis.For example,extended periods(over hundreds of millions of years)of sulfidic bottom water are found in basinal settings within the Mesoproterozoic(Shen and others,2002,2003).Also,there is evidence for the transition from iron-rich to sulfide-rich bottom water in sediments just overlying the Gunflint Formation,represent-ing one of the last early Proterozoic episodes of BIF deposition(Poulton and others, 2004).Also,from Mo isotope studies of sediments from the McArthur Basin,Arnoldand others (2004)conclude that a substantial portion of the global ocean was sulfidic between 1.4and 1.7Ga.If the sulfidic middle Proterozoic ocean model is correct,the subduction of pyritized terrigenous deep-sea sediments was a significant sulfur removal pathway from the surface reservoir,and this pathway may have been important from 1.8Ga to about 0.7Ga.Furthermore,deep-water anoxic conditions would have inhibited seafloor weathering reactions,and relatively low ocean sulfate concentra-tions of probably around 2mM,as inferred by Shen and others (2002),would have limited the high temperature inorganic reduction of seawater sulfate atmid-ocean Fig.3.The sulfur cycle is shown during different periods of Earth history.The dashed lines represent pathways that are either substantially suppressed or are inoperative with the particular conditions of ocean and atmospheric chemistry of the time:(A)the sulfur cycle during periods of the Archean and early Proterozoic,when the oceans were iron rich.During this period the sulfide subducted was mostly derived from hydrothermal sulfide inputs.Atmospheric oxygen was also low,(B)the sulfur cycle during periods of the Proterozoic when the oceans were sulfide rich.Here,the sulfide subduction rate is controlled by the subduction rate of reactive Fe-containing continental clastics,(C)the sulfur cycle during the last 0.7Ga where the ocean was oxic.Sulfide subduction is suppressed without bottom water anoxia.See text and table 2for further details.Symbols are the same as those in figure 1.847sulfur reservoirspreading centers.An outline of the sulfur cycle from about 0.7to 1.8Ga,with sulfidic deep-water,is shown in figure 3B.Beginning around 0.7Ga,at least periodic oxygenation of the deep ocean was likely (Canfield and Teske,1996),and although several periods of deep-water anoxia existed in the Phanerozoic (for example,Berry and Wilde,1978),it is assumed that over the last 0.7Ga the deep ocean remained dominantly oxygen-rich,and sulfate-rich.As we shall see below,there was probably not a rapid increase in seawater sulfate concentrations at 0.7Ga.Nevertheless,we assume a step function for simplicity in modeling.In switching to oxic ocean bottom waters,the removal of sulfur by the subduction of deep-sea sediments becomes negligible,and the oxidation of ocean crust during hydrothermal circulation provides a new source of sulfur to seawater.The only sulfur sink into the mantle is the incorporation of seawater sulfate,reduced to sulfide,and fixed in the ocean crust during high temperature hydrothermal circula-tion (see above).As mentioned above,sulfate reduction during serpentinization is another potential sulfate sink,but its magnitude may well be small and it is not considered here.A cartoon of the sulfur cycle over the last 0.7Ga is shown in figure 3C.Modeling Surface Reservoir SizeIn the following model,the processes controlling the fluxes of sulfur to and from the mantle are regulated by ocean and atmosphere chemistry as described above and as summarized in table 2.Furthermore,rates of volcanic outgassing,hydrothermal input,ocean crust weathering,and the removal rate of sulfur from high temperature sulfate reduction are scaled with the history of heat flow from the Earth interior (Turcotte,1980),which influences rates of tectonic activity.The model explores the scaling of these fluxes both linearly as a function of heat flow and as a function of heat flow squared.Plate velocity scales with heat flow squared if the mantle is modeled as a convecting layer with strongly heat-dependent viscosity (Gurnis and Davies,1986).As some of the exchange processes may vary with plate velocity,a squared functionality is also explored.The history of heat flow is approximated relative to today (Q rel )with equation (2),where t is time before present in Ga.Q rel ϭ1.00ϩ0.1217t ϩ0.0942t 2.(2)Table 2A summary of ocean chemistry and the presence or absence of mantle sulfur inputs and outputs overtime.ain some models the magnitude has been reduced to simulate the subduction of a portion of the input back into the mantle.b all of the hydrothermal input is assumed to be subducted back into the mantle when this pathway is active.c only includes the sulfide from the pyritization of terrigenous sediment particles when the ocean is sulfide rich.d switched on at the Cambrian-Precambrian boundary (0.54Ga)in light of evidence for low late Neoproterozoic concentrations of sulfate (see text).e direct volcanic outgassing to the atmosphere and surface environment.Does not include hydrothermal flux at ocean spreading centers.848 D.E.Canfield—The evolution of the Earth surface。

专利名称：The light absorption 发明人：鴫原 秀勝,高見 学申请号：JP2002063587申请日：20020308公开号：JP3989750B2公开日：20071010专利内容由知识产权出版社提供摘要：PROBLEM TO BE SOLVED: To provide a liquid crystal display device with high contrast and excellent visibility and a light guide to be used for the liquid crystal display device by eliminating space parts on respective bonded surfaces of laminated members.SOLUTION: A light guide layer consisting of a silicone resin sheet 11 or a light guide layer consisting of a light guide material composed of a synthetic resin held between two pieces of the silicone resin sheets 11 is constructed. The light guide comprises a light source 12 disposed on an end face part of the layer so as to make light incident on the inside of the layer from the end face (1). The liquid crystal display device comprises a liquid crystal display cell 16 having a liquid crystal 9 for forming pixels disposed between two pieces of substrates 7, 8 with electrodes arranged thereon, the light guide and a touch panel 15 successively laminated from the side farther from the viewer wherein differences of refractive indexes at 550 nm wavelength between members of the respective bonded surfaces intervening between the liquid crystal display cell 16 and the light guide and the transparent touch panel 15 and the light guide are 0.1 or less (2).COPYRIGHT: (C)2003,JPO申请人：ナノックス株式会社地址：福島県福島市岡島字長岬６―７国籍：JP代理人：松永 孝義更多信息请下载全文后查看。

专利名称：CO2 laser stabilization systems and methods发明人：Boris Grek,Michael Weitzel,Igor Landau申请号：US11054052申请日：20050209公开号：US20060176917A1公开日：20060810专利内容由知识产权出版社提供专利附图：摘要：Systems and methods for stabilizing a COlaser are disclosed. The systemincludes a detector unit for measuring the power in a select portion of the output beam.The detector unit generates an electrical signal corresponding to the measured power.The modulation frequency of the signal used to modulate the relatively high-frequencyradio-frequency (RF) pump signal is filtered from the electrical signal. The filtered electrical signal is then compared to a desired value for the output power in the output beam. Based on the comparison, a modulation control signal for modulating the RF pump signal is formed. The modulation control signal has a varying duty cycle that varies the amount of laser pump power to reduce or eliminate the measured variations in the output beam power. The result is an output beam power that remains stable over time.申请人：Boris Grek,Michael Weitzel,Igor Landau地址：Hayward CA US,San Jose CA US,Palo Alto CA US国籍：US,US,US更多信息请下载全文后查看。

专利名称：Gas-discharge display panel and process formanufacturing the display panel发明人：Noriyuki Awaji,Shinji Tadaki申请号：US10698408申请日：20031103公开号：US06921310B2公开日：20050726专利内容由知识产权出版社提供专利附图：摘要：A display panel is provided that has a multilayer structure made of a colored glass layer having a desired shape and optical characteristics and a non-colored glass layer having high transparency, as well as high productivity. The display panel has a non-colored glass layer and a colored glass layer contacting the non-colored glass layer. A multilayer structure is formed that includes a colored paste layer and a non-colored paste layer. In the colored paste layer, crystallization glass powder that is crystallized at the temperature TA and coloring agent are diffused. In the non-colored paste layer, glass powder whose softening point is the temperature TB that is higher than the temperature TA. The multilayer structure is heated to the temperature TC that is higher than the temperature TB and is lower than the softening point of the crystallization glass powder after the crystallization to be burned, so that the non-colored glass layer and the colored glass layer are formed simultaneously.申请人：Noriyuki Awaji,Shinji Tadaki地址：Kawasaki JP,Kawasaki JP国籍：JP,JP代理机构：Staas & Halsey LLP更多信息请下载全文后查看。

专利名称：Gas-discharge display panel and process formanufacturing the display panel发明人：Noriyuki Awaji,Shinji Tadaki申请号：US10698408申请日：20031103公开号：US20040102126A1公开日：20040527专利内容由知识产权出版社提供专利附图：摘要：A display panel is provided that has a multilayer structure made of a colored glass layer having a desired shape and optical characteristics and a non-colored glass layer having high transparency, as well as high productivity. The display panel has a non-colored glass layer and a colored glass layer contacting the non-colored glass layer. A multilayer structure is formed that includes a colored paste layer and a non-colored paste layer. In the colored paste layer, crystallization glass powder that is crystallized at the temperature TA and coloring agent are diffused. In the non-colored paste layer, glass powder whose softening point is the temperature TB that is higher than the temperature TA. The multilayer structure is heated to the temperature TC that is higher than the temperature TB and is lower than the softening point of the crystallization glass powder after the crystallization to be burned, so that the non-colored glass layer and the colored glass layer are formed simultaneously.申请人：FUJITSU LIMITED更多信息请下载全文后查看。

专利名称：Photovoltaic perovskite material andmethod of fabrication发明人：Jinsong Huang,Qingfeng Dong,RuiDong,Yuchuan Sao,Cheng Bi,QiWang,Zhengguo Xiao申请号：US14576878申请日：20141219公开号：US09391287B1公开日：20160712专利内容由知识产权出版社提供专利附图：摘要：A semiconductor device and a method for fabrication of the semiconductordevice are described that include a perovskite layer formed using a solution process with lead iodine and methylammonium halide. In an implementation, a semiconductor device that employs example techniques in accordance with the present disclosure includes a cathode layer; an anode layer; and an active layer disposed between the cathode layer and the anode layer, where the active layer includes a perovskite layer including an interdiffused and annealed lead iodine (PbI) film and methylammonium halide (CHNHX) film. In implementations, a process for fabricating a continuous-perovskite semiconductor device that employs example techniques in accordance with the present disclosure includes spinning a PbIlayer onto an ITO-covered glass; spinning an MAI layer onto the PbIlayer; annealing the PbIlayer and the MAI layer; spinning a PCBM layer onto a resulting perovskite layer; and depositing an Al layer.申请人：The Board of Regents of the University of Nebraska地址：Lincoln NE US国籍：US代理机构：Leydig, Voit & Mayer, LTD更多信息请下载全文后查看。

专利名称：SENSOR SYSTEM发明人：TOMAGO, Norihiro,IMAI, Kiyoshi,IIDA, Yusuke,SHIBASAKI, Yusuke申请号：EP19800792申请日：20190425公开号：EP3792892A4公开日：20220112专利内容由知识产权出版社提供摘要：An objective of the present invention is to provide a sensor system with which a change in the state of a workpiece which has occurred in a conveyance process can be determined. Provided is a sensor system comprising: a plurality of sensors positioned along a line and measuring data indicating that a workpiece being conveyed upon the line has passed thereby; a plurality of slave units respectively connected to the plurality of sensors and acquiring the data measured by the plurality of sensors; and a master unit connected to the plurality of slave units. The master unit comprises: a storage part for storing the data in association with information which relates to the timing at which the data was measured; and a determination part for comparing the data transmitted from two or more of the plurality of slave units using the information which relates to the timing, and determining a change in the state of the workpiece.申请人：OMRON Corporation更多信息请下载全文后查看。

《海相碳酸盐阴极发光性的控制因素》读书报告学生：** 学号：2008020** 指导老师：黄思静1．阴极发光原理阴极发光法是通过电子轰击真空样品室中未盖片的薄片或岩块来实现的，这种轰击产生了包括可见光在内的电磁波辐射，从而揭示出被轰击样品的特征。

碳酸盐岩类的阴极发光性是由于微量元素的存在引起的，通常表现为黄-红色(波长540—675 nm)。

已知Mn是方解石和白云石中最为有效的发光激活剂，而Fe则是发光的猝灭剂。

2．碳酸盐矿物发光特征碳酸盐造岩矿物主要有四种，即方解石CaCO3、白云石。

CaMg(CO3)2、菱镁矿MgCO3、菱铁矿FeCO3，它们均属三方晶系，具有两组完善的菱面体解理，薄片中无色透明，具有较高的正突起，呈高级白干涉色。

而在阴极发光当中具有明显不同的发光特征。

方解石常见的阴极发光颜色为橙色、橙黄色、橙红色，少数阴极发光为兰黑色、白一淡黄色、及白一淡绿色。

低镁方解石为鲜橙色，高镁方解石暗红色，合成方解石为粉红色。

取自含海百合茎、苔鲜虫类、介形虫生物碎屑灰岩中的方解石为黄橙色。

白云石多为淡红褐一暗红褐色，紫色及玫瑰红色也比较常见，在大理岩中的白云石往往呈白一淡黄色、淡红色以及淡紫色;在白云岩化鲡状灰岩中的白云石，边缘为暗红褐色，中心为浅红褐色。

菱镁矿Mg CO3阴极发光为红色、玫瑰红色，也有的为兰色和亮兰色。

菱铁矿Mg CO3，阴极发光为橙色。

3．微量元素的控制作用碳酸盐岩阴极发光特征主要通过两项指标衡量：发光强度和发光颜色。

发光强度是指在电流、电压、放大倍数相同情况下,矿物发光的明暗强度。

根据前人的研究来看，影响碳酸盐矿物阴极发光特征的主要因素为激活剂和岩石产状。

Mn2+、Fe2+、Pb2+、S2+是影响碳酸盐阴极发光特征的主要离子。

但主要受Mn2+和Fe2+含量,以及Mn2+/Fe2+值的综合控制。

Mn2+含量对发光的影响Mn2+为碳酸盐矿物阴极发光的激活剂。

关于碳酸盐矿物发光所需Mn2+含量的下限,前人进行了研究。

碳酸盐岩中阴极发光的激活作用及发光环
带
在碳酸盐岩中，阴极发光（cathodoluminescence，简称CL）是一种由阴极射线激活的发光现象，它是碳酸盐岩中离子激发和自发发光的结合体。

这种发光可以帮助研究人员更好地了解岩石的成因和结构，以及矿物的鉴定和分析。

在碳酸盐岩中，阴极发光的激活作用是由阴极射线激发的，这些射线能够激活碳酸盐岩中的矿物结构，从而产生发光。

发光的强度取决于碳酸盐岩中矿物的种类和含量，以及阴极射线的能量和时间。

此外，阴极发光还可以形成发光环带，这种环带是由碳酸盐岩中的矿物结构和阴极射线的能量和时间共同作用下形成的。

发光环带的形成可以帮助研究人员更好地了解碳酸盐岩的成因和结构，以及矿物的鉴定和分析。

因此，阴极发光在碳酸盐岩中的激活作用和发光环带的形成可以帮助研究人员更好地了解岩石和矿物的结构和成因。