Surface Instability in Windblown Sand
WESP
Richard C. Staehle and Ronald J. TriscoriK. Sampath (Sam) Kumar The Babcock & Wilcox CompanyF.L. Smidth Airtech Inc.Barberton, Ohio, U.S.AHouston, Texas, U.S.A Gary RossEd Pasternak New Brunswick PowerAES Deepwater Fredericton, New Brunswick, CanadaPasadena, Texas, U.S.AThe Past, Present and Future of Wet Electrostatic Precipitators in Power Plant ApplicationsPresented toBR-1742Combined Power Plant Air Pollutant Control Mega Symposium May 19 - 22, 2003Washington, DC, U.S.A.BackgroundWet electrostatic precipitators (WESPs) have been commer-cially available since their first introduction by F.G. Cottrell in 1907. However, most of their use has been with small, industrial-type settings as opposed to electrical utility power plants. In the past 20 years, this technology has been applied periodically to electric power plant sources.In electric utility plants firing sulfur-bearing fuel, wet flue gas desulfurization (WFGD) and, in the past decade, selective catalytic reduction (SCR) technologies have been added to control sulfur dioxide and nitrogen oxides emissions. The recent start-ups of new SCR systems on coal-fired power plants have demonstrated an increase of sulfuric acid emissions due to the oxidation of a portion of SO 2 across the SCR catalysts .1 Although the control of sulfuric acid mist from electric utility sources has typically not been regu-lated, concern and questions regarding these emissions are now being observed.The combustion of petroleum coke or Orimulsion TM with rela-tively higher concentrations of vanadium (a catalyst for the oxida-tion of SO 2 produced in combustion to SO 3) produces high levels of sulfuric acid emissions, in some cases as high as at power plants firing high sulfur coal.2In cases where the wet FGD technology is utilized in conjunc-tion with SCRs on high sulfur coals or with high vanadium petro-leum fuels, the condensed sulfuric acid component in the flue gas can exceed 20 ppmvd @ 3% O 2. This causes a pronounced stack opacity because of the inherent light scattering properties of the sub-micron particulates.3 Acid mist concentrations as low as 5 to 10 ppmvd have caused visible plume problems.This paper will discuss the past application of WESP technol-ogy, recent experiences that pertain to the electric utility industry,and economic analyses of WESP application to address potentialand future utility needs. The analyses compare the WESP to the alternative approach of sorbent injection to control acid mist emissions.Past WESP ExperienceAs stated above, WESPs have been serving the needs of metal-lurgical industry and many other applications for nearly 100 years,to control sulfuric acid and particulates. More than 1000 WESPs are in worldwide commercial operation today.4 There are several configurations of WESP designs now proven in commercial prac-tice. WESPs are made of tubular and parallel-plate type collecting electrodes. While the tubular WESPs will have only vertical gas flow orientation (upflow or downflow), the plate type designs can have either horizontal gas flow or vertical gas flow orientation.Materials of construction have long been a major issue in WESP design for metallurgical applications. In copper roasters, for ex-ample, the SO 2 concentrations in off-gases often exceed 10% be-cause of high pyritic content in the ore. Environmental regulations that reduced SO 2 emissions from these sources led to the commer-cialization of converting this rich, SO 2 laden gas stream into a us-able resource – sulfuric acid. Ironically, the WESP technology also protected the process’ vanadium oxidation catalyst from being “poi-soned” and plugged by reducing the particulates and SO 3 prior to entering the acid plant. The WESPs became the workhorses for the industry in collecting sulfuric acid mist. WESPs also removed trace elements, such as arsenic, to enhance the quality of sulfuric acid made in the acid plant.In the 1940s, the typical WESP design for acid mist control commonly used corrosion-resistant lead collection surfaces (both plate and tubes), lead-lined mild steel high voltage systems, and casings comprised of skeleton steel structures with lead burnedover the steel surfaces for protection from the acid gas stream. Due to the structural weakness of the lead and the operating pressures of downstream acid plants, leaks would occur and soon the skel-eton steel structure underwent corrosive attack and failed. Addi-tionally, corrosion-resistant lead materials were shown to be sus-ceptible to mechanical failure when used at operational tempera-tures above approximately 150°F. Eventually, the casing design evolved to alternatives such as fiberglass reinforced plastic to house the lead and lead-covered internals. This new design improved the life cycle of the WESPs and also minimized the need for highly skilled lead burner craftsmen. During this same timeframe, some manufactures started using plastic and FRP collecting electrodes to further minimize the lead content of their designs. In the 1970s some manufacturers began using specialty stainless for any lead-covered components that remained in their designs. The main driv-ing forces behind these evolutions were problems associated with the use of lead, including the specialized construction and mainte-nance labor required, reliability and maintenance/repair costs, and the ever growing concern over lead toxicity.There has been a recent report of a toxics release at a metallurgi-cal plant as a result of a fire within a WESP that used polypropy-lene collecting tubes and FRP casing. This type of experience has raised concern in other plants using plastic WESP components.Therefore, given the above, it is anticipated that electric utility power plants may understandably show a reluctance to use lead or plastic components in their WESPs.During the 1970s and 1980s, the successful use of alloy in wet FGD inlet sections and outlet flues provided sufficient confidence in the further use and applications of alloys. Today, alloy steels including 317, 6% molybdenum and C-276 grades are being used routinely in wet FGD systems.What has emerged from these past applications is a strong expe-rience base to design WESPs for high efficiency control of sulfuric acid and particulates for electric utility applications. The base in-cludes both horizontal flow and vertical flow WESPs. Both designs have been shown to achieve high efficiency collection. Site-specific questions regarding WESP layout and physical integration into the gas cleaning system will ultimately decide the best economic choice.One of the process issues that has surfaced during WESP opera-tion, when dealing with sulfuric acid mist, is a phenomenon known as corona suppression. Corona suppression is not new to electro-static precipitation. Formation of SO3 vapor together with flue gasmoisture will create ultra-fine particles of sulfuric acid mist. This mist can severely suppress operating corona current in the WESP. If present, the corona suppression will decrease collection effi-ciency in the WESP. Factors that cause or aggravate this condi-tion in a WESP following a wet FGD are large concentrations of fine sulfuric acid mist droplets and a high degree of water mist condensation.5The above effect can be made even more of a problem by im-proper choices in the design of ESP collection and discharge elec-trode geometries. By choosing a discharge electrode geometry ex-hibiting a low corona onset voltage, and by limiting the distance between corona electrode and collecting electrode, corona current can be established and maintained at adequate levels in the inlet fields. This reduces the fine particulate loading exiting the inlet field, thus permitting operation with sufficient power levels in the downstream WESP fields to achieve the overall design collection efficiency. Management of corona suppression is enabled due to past experiences with WESPs but also with dry ESPs on other applications that exhibited the corona suppression problem, such as saltcake (principally sodium sulfate salts) from chemical recov-ery boilers and dry cement kilns (where fine particulates are foundin high concentrations).6Recent WESP ExperienceAES Deepwater, TexasAES Deepwater is a petroleum coke fired cogeneration plant located on the Houston Ship Channel in Pasadena, Texas. The plant generates approximately 155 MW of electricity.2This plant utilizes a dry electrostatic precipitator to limit the levels of particulates and unburned carbon entering the limestone-based, gypsum-producing wet FGD system. This plant also uses a wet venturi scrubber prior to the wet FGD to remove additional particulate, HF and HCl. While particulate limits are necessary for regulatory compliance, control of unburned carbon is required to prevent contamination of salable by-product gypsum.The petroleum coke fuel has a high vanadium content, which results in relatively high level of SO3entering the wet FGD where the gas quenching action completes the formation of sulfuric acid mist. Only about 20-30% of the mist is captured in the FGD sys-tem because of the fine particle size of the mist droplets. The inletconcentration of SO3varies between 35 to 100 ppmvd @ 3% O2 depending on furnace operating conditions and vanadium content in the petcoke.AES has the oldest operating U.S. installation of a WESP in a power plant application. Table 1 shows the design information and required emission levels. The limit for total particulates including sulfuric acid and condensable was set for 0.005 grains/scfd, thus requiring a collection level of greater than 90% on sulfuric acid alone. Particulate control across the WESP is, typically, in the 95 to 97% range. This is in addition to the high efficiency collection of the dry ESP and the wet venturi scrubber ahead of the wet FGD. Such high efficiency, total particulate control across the system was necessary in 1986 to meet the stringent limits required in this non-attainment area. While the State of Texas required sulfuric acid emissions control to meet the tight particulate limits, to this day there are no federal standards for the control of sulfuric acid mist emissions from such sources.This WESP design consists principally of a three field, upflowTable 1 Specifications for air pollution control systeminstalled at AES DeepwaterDry ESPInlet gas flow634,000 ACFM at 360°FSCA376 ft2/1000 ACFMPart. collection efficiency97%FGDSO2removal efficiency90%Pre-scrubber/Quencher Venturi type, downflow/co-current Tower gas velocity9 ft/secMist eliminator Two-stage, chevron typeStack gas reheat To 175F w/in-line steam reheater Calcium sulfite oxidation Bleedstream pressure oxidationin separate towersWet ESPGas velocity7.7 ft/secTreatment time 4.2 secSO3,ppmv dry @ 3% O230 to 100Part. collection efficiency98.9% including sulfuric acid mist Outlet loading stopper0.005 grains/scfd, including sulfuric acidsystem of 12 parallel modules. The collection surfaces are plate-type, fabricated of balsa wood coated with reinforced thermoset plastic. The plates are kept irrigated, for electrical conductivity and removal of collected matter, by a continuous film of water flowing down over the surfaces of the plates. A system of collection trough gutters at the bottom of collector plates removes irrigation water and collected matter from the WESP.This WESP system has been in successful commercial opera-tion since 1986. Particulate limits were met, and stack opacity is generally maintained well below 10%.The discharge electrodes and other high voltage internals were made of alloy C-276. After more than 15 years of operation these internals appear new, with no observable signs of corrosion.In 1999, all of the original collection plates in 1 of the 12 mod-ules were removed and replaced with new alloy collector plates made of 6% Mo stainless steel. AES wanted access to higher per-formance and lower maintenance cost technology should the need arise in the future. The discharge electrodes in this module were also changed out from the original round wires to higher corona forming strip-type high voltage discharge electrodes. Figure 1 shows the configuration of module B that was retrofitted with alloy col-lector plates. Figure 2 shows the current-voltage relationship from the inlet to outlet fields. It is seen that corona current increases significantly from the first field to the third field, which is indica-tive of the effective management of corona suppression, existing though not serious, because of the presence of the sulfuric acid mist fines. While collection performance of the WESP is not an issue, there potential for an even higher corona producing inter-electrode geometry for this unit.After more than three years of operation on this retrofitted module with all alloy WESP collecting and discharge electrodes, the 6% Mo collector plates have shown no corrosion and still appear as they did when new.Northern States Power/Xcel EnergyThere are twenty four (24) WESP modules installed at this plant, twelve (12) each on the two 750 MW units. The plant chose the WESP solution to limit its stack opacity below 20%. The approach was to retrofit an upflow, two-field WESP inside an existing casing made available by re-positioning the particulate scrub-ber internals. Following an initial trial evaluation of WESP technol-ogy, the across-the-board retrofit of WESPs began in 1998 and was completed in 2001.Xcel Energy’s Sherbourne County Station is burning sub-bitu-minous coals having about 20% CaO available in the flyash. The free CaO in this flyash acts to absorb the SO3in the flue gas. The original high energy, combined particulate/SO2wet scrubbers alone were unable to limit stack opacity below 20%. There are no dry ESPs installed on these units. By using WESPs, the stack opacity has been limited to levels about 10% as compared to pre-WESP levels of 40%.7 Particulate control exceeding 90% has been achieved with the one second residence time available within the WESPs’treatment zones.Due to the high calcium content of the flyash, material scaling occurs in the bottom portion of the first field collector tubes. The first fields primarily capture the re-entrained droplets and carryover from the upstream scrubbers, thus allowing for relatively stable electrical operation in the second fields for fine particulates cap-ture. Each of the modules gets a thorough, off-line manual high pressure washdown about once a year to remove scale. In addition, part of normal daily operation includes a water flushing of modules while the power supplies are de-energized. The alkaline nature of flyash and absence of sulfuric acid mist allowed the use of 304 L for the WESP internals for this application. Lessons learned from this experience are: 1) WESP is able to overcome difficult conditions for dust build-up through well scheduled wash downs, and 2) high efficiency non-acid particulate collection, in addition to sulfuricacid mist collection, is an important capability to consider when evaluating WESPs for sulfuric acid collection.Northwestern U.S. Petroleum RefineryA petroleum coke calciner produces flue gas containing SO 2 that is treated with a caustic reagent scrubber. While the scrubber is highly efficient in absorbing SO 2, it cannot adequately capture the sulfuric acid mist. Since 1998, a WESP has been used to achieve a high degree of sulfuric acid capture to eliminate the visible plume.Three parallel WESP modules in a single field, upflow configura-tion are utilized. Figures 3 and 4 show the excellent particulate and sulfuric acid capture across the WESP. Sulfuric mist emissions were limited to levels of approximately 1 ppmvd @ 7% O 2, and particulate concentrations were reduced to levels well below 0.005grains/scfd.The material of construction of these WESPs’ internals and casing is alloy 904 L. The corrosion resistance has been very good,once again, observably in “like new” condition upon inspection.New Brunswick Power, Coleson CoveIn 2002, New Brunswick Power elected to install high effi-ciency WESPs following two new limestone-based wet FGD scrub-bers at their 1050 MW Coleson Cove station. This was part of a plantwide effort to reduce the cost of electricity generation by switching to lower cost Orimulsion TM fuel while considerably re-ducing SO X and particulate emissions. New Brunswick Power’s decision to install the WESPs was to assure control of sulfuric acid emissions below 5 ppmvd @ 3% O 2, and limit flyash particulates below 0.015 lb/MBtu. To achieve this level of control on sulfuric acid at all times, collection efficiency requirements will exceed 90%.Coleson Cove will be the second power plant at which New Brunswick Power has installed a WESP system for the collection of acid mist following a wet FGD. A smaller, single-field WESP system went into operation at its Dalhousie plant in the year 2000which followed that plant’s conversion to Orimulsion TM firing and wet FGD installation in 1994.Figure 5 shows a schematic of the layout for the Coleson Cove plant for each of the two wet FGD absorbers. It can be seen that the wet ESP consists of a three field upflow design, similar to the design that has been in successful use for more than 15 years at the AES Deepwater facility. Scrubbed flue gas enters the inlet field of WESPs after exiting the wet FGD mist eliminator.There are three electrical fields in series and four independently energized high voltage bus sections across each WESP electrical field. This conservatively sectionalized, twelve (12) bus section design allows for small sections to be de-energized during periodic water flushings while maintaining overall emissions within design levels.Figure 3 WESP data on sulfuric acid from refinery in northwest U.S.Figure 4 WESP Data on Particulate from Refinery in northwest U.S.Figure 2 I/V data from AES WESP.The gas exits the top of the WESP through a final mist elimina-tor section which captures any re-entrained droplets that may be present during flushing cycles, and transitions directly into the stack through an outlet hood. This design simplifies and lowers the balance of plant costs which would otherwise be associated with a conventional arrangement where the WESP may be placed on a stand-alone basis and outside of the wet FGD vessel.The Coleson Cove plant is located on a shoreline, where layout space was at a premium. Therefore, this integrated arrangement between the wet FGD absorber and WESP made the most sense.The material of construction of collecting plates at the inlet field will be C-276. Stainless steel made of 6% Mo is utilized for the high voltage systems and the balance of the collection plates.Construction of the integrated wet FGD/WESP systems will begin in spring of 2003. The systems will be operational by Sep-tember 2004.It is expected that this integrated, multi-pollutant approach to wet FGD installations will become more common in future fossilfired power plants and as a retrofit where multiple control of NOX ,SOX , mercury and fine particulates of flyash and sulfuric acid maybe required.Comparison of WESP Versus Sorbent In-jection OptionsStudies have investigated the possibility of sulfuric acid emis-sion reductions through the use of additives that allow existing air pollution control equipment to trap the resultant particulate mat-ter. In this way, the retrofit of another piece of capital equipment such as the WESP could be avoided.A pilot testing study commissioned by the Electric Power Re-search Institute (EPRI) at its high sulfur test center in New York more than ten years ago is still relevant to determine the effective-ness of various sorbents for the removal of SO3and its associated plume.9 More than ten years later, a full-scale evaluation was com-missioned by American Electric Power at its Gavin station to evalu-ate the effectiveness of control of sulfuric acid mist following the installation of retrofitted SCRs.1, 10 This installation also has anexisting wet FGD system for SO2control.A summary of the above studies is provided below and will be used as a basis to compare the economics of the alternatives:a.To remove SO3from flue gas in a utility boiler application, alkaline sorbents can be injected either in the upper furnaceor ahead of the dry ESP.b.Hydrated lime, ammonia and sodium bicarbonate were in-jected ahead of the dry ESP, while magnesium hydroxide wasinjected in the furnace sections.c.Injection of hydrated lime caused a significant loss of dryESP performance, which relies on the effect of free sulfuricacid for lowering flyash resistivity levels. Emissions wereincreased several fold due to increased flyash resistivity andparticulate loading to the dry ESP. Therefore, it may benecessary to consider the cost of ESP enlargement, or othermeans, to restore or improve the original particulate collec-tion performance.d.Injection of ammonia, while most efficient because of thegas/gas reaction for the absorption of SO3, affects dry ESP performance due to creation of ultra fine ammonium bisul-fate particulates. This can reduce the inlet corona current inthe dry ESP due to corona suppression. In addition, in-creased stickiness of ash can create ESP performance and/or maintenance problems and also ash handling systemproblems.e.There is motivation among the utilities to increase theamount of flyash utilization. Flyash utilization as cementraw material substitute is likely to show gains in energyuse, and thus contribute to the overall goal of CO2mitiga-tion. Both ammonia and sodium compounds in ash haveresulted in ash being unsuitable for use. In several plantsthat are already utilizing a salable flyash, this presents adouble problem of loss of ash revenue and increased costof ash disposal. (This impact will be included for analysiswhen evaluating sodium based sorbents.)f.Magnesium hydroxide injection in the furnace yields resultssimilar to hydrated lime injection ahead of the ESP.Economic Evaluation of Alternatives The following evaluation focuses on comparing the cost of WESP technology versus sodium bicarbonate and hydrated lime injection. The results for magnesium hydroxide and ammonia have a similar impact, the former being analogous to lime and the latter to sodium bicarbonate.The capital cost of wet ESP is annualized, and added to this are anticipated annual operating costs to generate the annual cost to own and operate the WESPs. A capital recovery factor of 0.1 is used to generate annualized cost of capital. For a levelizing period of 15 to 20 years, and a difference between interest and discount rates of 6%,this factor is considered reasonable and conforms within EPRI guide-Figure 5 Upflow WESP integrated with WFGD.lines. Operating costs for WESP power supplies, controllers, and high voltage insulator heaters are included in the evaluation.Comparison is made of the WESP annual costs to the annual-ized cost of sorbent injection technology. Impacts of ESP enlarge-ments and loss of ash sale are included as appropriate.Table 2 shows the estimated total installed cost of WESP of the design as shown for Coleson Cove for three different levels of collection efficiency. For a 50% collection efficiency, a single field unit will suffice. For a collection efficiency requirement of 80%, a two field unit will be necessary. For achieving collection efficiency of sulfuric acid exceeding 90% collection, a three field unit will be required.Table 3 shows the injection rates of dry hydrated lime andsodium bicarbonate to achieve the above mentioned SO3 collectionefficiency levels. It is readily seen that required injection ratesincrease rapidly as the SO3 collection efficiency requirements ex-ceed 50%.In the sorbent injection approach it is assumed that an injection temperature of 310°F is maintained. It is known that increasing the residence time to aid gas/solids mixing ahead of the dry ESP will reduce sorbent injection rates and associated costs. It is further as-sumed that this situation already exists at the plant. Additional costs may be incurred for ductwork modifications if this situation does not exist and provisions for increased residence time are required.The following assumptions are made in the analysis:• A 500 MW unit is considered in this example.•An existing dry ESP of 250 SCA (ft2/1000 ACFM) is keep-ing particulate limits below 0.03 lb/MBtu.•Additional 30% increase in treatment time will be needed to restore the ESP performance after lime sorbent injection.•Ash disposal costs are at 10$/ton of ash.•Ash utilization of 50% of the ash can be done at this plant ata price level of 5$/ton ash.•Bituminous coal results in ash content into the ESP of 10 lb/ MBtu.•The plant operates 8000 hours per year.•Hydrated lime can be purchased for 100 US$/ton delivered.•Sodium bicarbonate can be purchased for 250 US$/ton deliv-ered.Table 4 shows the annualized costs to own and operate the WESPs, dry lime system and sodium bicarbonate system. It is seen that if a particular plant must maintain its ash sale, or maintain its pre-injection particulate limits after sorbent injection, the WESP has considerably lower cost to own and operate when compared to the sorbent injection techniques shown here. This is true for the levels of SO3collection efficiency discussed above.The fact that total particulate emissions from the WESP are several times lower than the dry solution is not factored into this economic analysis.The economics favor the WESP technology even more for the 80% and 90% removal cases, because the sorbent utilization effi-ciency decreases for higher levels of SO3removal. Again, no credit has been applied to the WESP technology to reflect the fact that stack particulate emissions are much lower than with the sorbent technology.An additional factor that may promote the use of WESP tech-nology is that droplet carryover from the wet FGD is captured at a high efficiency in the WESP. To the extent soluble ionic mercury is readily captured in the wet ESP, overall system improvements in mercury capture are to be expected. This mechanism is unavailable in the sorbent injection technology.Conclusions•WESPs have been a proven technology for the collection of sulfuric acid mist for nearly 100 years.•The use of WESPs to limit total particulates, including sul-furic acid mist, in conjunction with a wet FGD system isbecoming increasingly relevant to electric utility plants.•WESPs integrated with wet FGD absorbers are an economi-cal alternative in terms of capital and operating costs, andplant layout restrictions, when compared to “stand-alone”WESPs.•In spite of the higher capital costs, WESPs are more eco-nomical to own and operate when compared with hydratedlime and sodium bicarbonate injection technologies.•Power plants should consider impacts of sorbent injection technologies due to potential loss of ash sales, as well asadverse impacts on the dry ESP performance.•The additional benefits in keeping solid particulates at very low levels, and possible benefits in mercury control, willmake the WESPs a desirable choice when considering theavailable options for SO3control.•Requirements for future operating permits may address emis-sions of PM2.5, SO3and visible plume. WESP technology addresses all of these emissions.Table 2 Approximate total installed cost comparison of wet ESPs vs. SO3Collection Efficiency (500 MW Plant)Number of fields SO3Collection efficiency, %$/kW150202803039540 Notes:1.These values based on 6% Mo internals.2.$/kW figures based on “greenfield” construction maximizing modular construction.3.$/kW figures based on the WESP component portion of a total WFGD/WESP integrated system.Table 3 Sorbent injection rates for achieving stated levels ofSO3removalSorbent type, SO3collection efficiency,% lb/hr/1000 ACFM50%80%95% Hydrated lime 1.536 Sodium bicarbonate35-Notes:1. Injection takes place ahead of the dry ESP around 300 to 350°F.2. All dry process.3. Capital costs of sorbent injection system estimated at 5$/kW.。
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iypt 2012 Sand_jets
124Sand jetsEliza BasińskaCreative Group QUARK, Poland, eliza.basinska@1 Purpose of the investigationWhen a heavy sphere is dropped onto a bed of loose, fine sand, a remarkable phenomenon occurs: a large, focused jet of sand shoots upwards. Although similar looking jets are observed on impact in fluid systems, they are held together by surface tension. Surprisingly, the granular jet exists in the absence of both surface tension and cohesion. My aim was to explain the behavior of the sand and describe the phenomena quantitatively.2 Method of the investigationFor my research I used a cylindrical container (0.5m high, 0.4m weight), filled with sand. After dropping the steel ball, we can observe the following series of visible events: first, the ball vanishes in the sand and a crown-like splash is created. Then, after a while, a jet shoots out of the sand at the position of impact. Finally, a granular eruption is seen at the position of impact, resembling a volcano.The first thing I was able to measure quantitatively, was the dependence between depth penetration and the kinetic energy of the ball. For the experiment, I have used 2 steel balls with different diameters.Scientists have already measured the behavior of the sand and a ball under the surface. They used composite x-ray imaging to show changes in local packing fraction after a metal sphere impacts a granular bed surface.3 Results of the experimentAs I written before, I have measured the dependence between depth penetration and the kinetic energy of the ball. The following diagram illustrates the results:Fig. 1 Depth penetration versus the height drop of the ball. The red dots denotes the results obtained for the ball which diameter was 1.2 [cm]. In the second experiment (blue dots) I have used 0.8 [cm] wide ball. Sand bed was 20cm deep.The axis x shows the height of a drop and theaxis y denotes the depth of the penetration. All values aregiven in centimeters.I was also able to vary the packing density of the sand in the container. Next diagram shows how depth penetration depend on the drop height of the ball and the packingdensity of the sand.Fig. 2 Depth penetration versus the packing density of the sand. The volume of the denser sand (blue dots) equaled 0.7 of the volume of loose sand (red dots).When the sand jet is falling down, we can observe the clusters and droplets formation. While the upper part of the jet is still going upwards, in the lower parts occur inelastic particle-particle collisions. This leads to density inhomogeneities in the jet.4 ConclusionsThis experiment shows that loose sand beds can sometimes behave like a fluid, although there is no surface tension. Jet height depends on many factors, eg. the initial height of the sphere, sphere diameter, compression of a sand bed and an ambient pressure.References[1]John R. Royer, Eric I. Corwin, Bryan Conyers, AndrewFlior, Mark L. Rivers, Peter J. Eng, and Heinrich M.Jaeger, “Birth and growth of a granular jet”, Phys. Rev.E 78, 011305 (2008)[2]John R. Royer, Eric I. Corwin, Andrew Flior, Maria-Luisa Cordero, Mark L. Rivers, Peter J. Eng and Heinrich M. Jaeger, "Formation of granular jets observed by high-speed X-ray radiography", Nature Physics 1, 164 – 167 (1 December 2005).。
如何设计高效催化剂
Surface Science Reports63(2008)487–513Contents lists available at ScienceDirectSurface Science Reports journal homepage:/locate/surfrepHigh-throughput heterogeneous catalysisDavid Farrusseng∗UniversitéLyon1,CNRS,UMR5256,IRCELYON,Institut de recherches sur la catalyse et l’environnement de Lyon,2avenue Albert Einstein,F-69626Villeurbanne,Francea r t i c l e i n f o Article history:Accepted16September2008 editor:W.H.Weinberg Keywords:CatalysisCombinatorial chemistryHigh-throughputKinetic modelingQSAR a b s t r a c tThis comprehensive review of the literature(over250references)deals with high-throughput experimentation in heterogeneous catalysis.Approaches to library design for catalyst discovery and optimization are described and discussed.Special focus is placed on advanced methods for knowledge discovery such as high-throughput kinetic modeling and QSAR.An inventory of successful case studies in catalysis is reported.Finally,recent developments in relevant electronic data and knowledge management are described.©2008Published by Elsevier B.V.Contents1.Introduction (488)2.Overview (488)3.Approaches to HT library design (489)3.1.The split&pool method (489)3.2.The hierarchical approach (490)3.3.Design of experiments(DoE)methodology(See also Figs.4and5) (492)3.4.Evolutionary algorithms (493)3.5.Evolutionary optimization using data mining tools (495)3.6.Summary (496)4.HT kinetic modeling (496)4.1.Reasons for conducting HT kinetic modeling (496)4.2.Technologies for HT kinetic modeling (497)4.3.Methodologies of HT kinetic modeling (497)4.4.Spatially-and time-resolved methods (499)5.The QSAR approach to catalysis (500)5.1.Generalities (500)5.2.Homogeneous catalysis and the QSAR approach (500)5.2.1.The QSAR concept (500)5.2.2.In silico generation of a virtual catalyst library (501)5.2.3.Choice and calculation of descriptors (501)5.2.4.QSAR modeling (501)5.3.Heterogeneous catalysis and the QSAR approach (502)5.4.HT physicochemical characterization for property quantification (502)5.5.Catalyst profiling using HT kinetic modeling of model reactions (503)5.6.Virtual screening through computational chemistry (504)Abbreviations:AniML,Analytical Information Markup Language;ANN,Artificial Neural Networks;ANOVA,Analysis Of Variance;DFT,Density Functional Theory;DoE, Design of Experiments;ee,enantioselectivity;FPA,Focalplane;FTIR,Fourier Transform Infrared;GA,Genetic Algorithm;GDC,Guided Data Capture;HT,High-throughput; HTE,High-throughput Experimentation;IT,Information Technology;KFE,Kinetic Fitting Engine;LRIS,Laboratory Research Informatic System;PCA,Principal Component Analysis;QM,Quantum Mechanics;QSAR,Quantitative Structure–Activity Relationship;QSPR,Quantitative Structure–Property Relationship;SCR,Selective Catalytic Reduction;SMEs,Small and Medium Enterprises;TPD,Temperature-programmed Desorption;TOF,Turnover Frequency;TON,Turnover Number;WGS,Water-gas Shift; WHSV,Weight Hourly Space Velocity;XML,Extensible Markup Language;XRD,X-ray Diffraction;XRF,X-ray Fluorescence.∗Tel.:+33472445365;fax:+33472445399.E-mail address:david.farrusseng@ircelyon.univ-lyon1.fr.0167-5729/$–see front matter©2008Published by Elsevier B.V.doi:10.1016/j.surfrep.2008.09.001488 D.Farrusseng/Surface Science Reports63(2008)487–5136.Discovery of catalytic materials by HT (504)6.1.Electrocatalysts for fuel cells (504)6.2.Selective hydrocarbon oxidation (504)6.3.Hydrogen production and purification (505)6.4.Automotive and refinery applications (505)6.5.Other applications (505)6.6.HT experimentation for zeolite synthesis and discoveries (505)7.Electronic infrastructure (506)7.1.Why automate data treatment? (506)7.2.Electronic open architecture for tool integration (506)7.2.1.HTE AG electronic platform (506)7.2.2.The NIST vision (506)7.2.3.Academic laboratories (507)7.2.4.Workflow-based electronic infrastructure for streamline data processing and knowledge management (507)7.2.5.Data normalization and e-standards in chemistry (509)8.Conclusions (509)Acknowledgements (510)References (510)1.IntroductionOver80%of commercial chemical processes involve the use of catalysis,with products as varied as chemicals,oil products, fertilizers,plastics,drugs and pharmaceuticals being made through catalytic steps.Catalysis is probably the most important means of producing modern chemicals;Europe’s chemical industry,for example,accounts for e1.5trillion,or14%,of this continent’s e10.5 trillion GDP(Gross Domestic Product).The likelihood of innovation in this field decreases,however, as catalytic chemical processes become increasingly mature. When new active solids are developed empirically,by trial-and-error processes employed on a few selected samples,the whole procedure is highly speculative and leads to a very slow rate of discovery for the industry in question.This research strategy based on exhaustive studies and complete understanding is also very time-consuming.Therefore,new research strategies have to be developed in order to produce breakthroughs and revitalize the field of chemical research.The high-throughput(HT)approach is a pragmatic alternative. It relies on the fast and systematic screening of libraries of diverse samples.This methodology is not new,since its origins can be found at different periods of the last century.One of the most striking examples is the discovery of the first ammonia synthesis catalyst by Mittasch et al.at BASF in1909followed by a‘‘systematic investigation of the periodic table’’with about 20,000experiments[1].This approach also appealed to K.Ziegler, who in the1950s applied it to the discovery of polymerization catalysts.The pragmatic approach of that time aimed at exploring and covering the periodic table;no references to HT screening or sample libraries could yet be made.We can trace the modern HT approach back to the pioneering work of Hanak in the1970s. He prepared and applied what we now call composition-spread or gradient libraries for research and development purposes at the RCA company laboratories.His work led to the successful entry of several new products onto the market[2].His vision of the experimental approach brought materials screening into the modern age:‘‘...the present approach to the search for new materials suffers from a chronic ailment,that of handling one sample at a time in the processes of synthesis,analysis and testing of properties.It is an expensive and time-consuming approach,which prevents highly-trained personnel from taking full advantage of its talents and keeps the tempo of discovery of new materials at a low level’’[3].The combinatorial principles employed in drug development were first applied to materials research in the early1990s by physi-cists and materials scientists at the Lawrence Berkeley National Laboratory of UC Berkeley.In fact,combinatorial materials sci-ence was recognized as a bona fide discipline only a few years later,following this team’s famous search for superconductors us-ing a materials library[4–7].By1997,the recently-formed Symyx Technologies had documented the state of the art of combinato-rial chemistry by publishing a library of over25,000distinct com-pounds[8].From2000onward,HT technology has been developed for and applied to an ever-increasing variety of materials,including electronic and magnetic materials,polymer-based materials,opti-cal materials,biomaterials,paints,drug formulations,detergents, cosmetics and glues,with the number of related publications and patents exploding accordingly.Today,HT experimentation has matured and is almost regarded as commonplace,its use in the development of new materials sometimes being omitted from a publication’s title or abstract,or even from the publication rge chemical companies (such as BASF,BP,Bayer,Degussa,DOW,DuPont,Exxon,GE, and UOP LLC)now generally have their own HT tools or labs. Meanwhile,smaller companies specialized in HT experimentation (such as Avantium,Bosch Lab Systems,hte AG,Symyx Technologies and Torial)have been founded,often enjoying spectacular growth in the space of the last ten years.Specialized companies such as these have succeeded thanks to their development of cutting-edge technologies,including hardware and software as well as their tight integration,that provide an impressive degree of throughput and productivity(number of samples screened per day and further decision making).In such a context of technological sophistication and high productivity,most academic groups have found themselves unable to compete in the race that is materials screening.Instead,public research centers can play a major role in HT by conducting fundamental research on domains as varied as synthetic methods,analytical tools,parallel in situ characterization,data mining and decision making processes and, finally–the focus of this review–screening strategies and methods.This review deals mainly with HT experimentation for hetero-geneous catalysis and also briefly discusses homogeneous cataly-sis.For other disciplines of materials science,the reader can refer to various reviews[9–19],books[20,21]and special issues[22–30]. An excellent summary of the state of the art for materials science has recently been published elsewhere[31].2.OverviewSince HT screening is a methodological approach,this review is divided into sections describing particular HT screening strategies and their associated strengths,issues,solutions,and case studies.What are the general issues affecting HT experimentation?D.Farrusseng/Surface Science Reports63(2008)487–513489Thanks to the modern screening techniques used in HT methods,dozens or even hundreds of experiments involving many variables can be performed at once.The inevitable combinatorial explosion that results leads to two urgent,fundamental questions relating to experimental design:which experiments are the most relevant to carry out,and what is the most efficient screening strategy?Data analysis is the next issue to come up after the experimental design is chosen.It is hardly possible for humans to fully evaluate results and statistical trends emanating from data sets involving more than four variables and20experiments.The issue of decision making takes on particular importance in such a scenario.In order to understand a catalytic process,one must be aware of the most relevant variables and combinations of variables affecting it.Catalysis,and chemistry in general, are matters of synergy and typically involve highly non-linear behaviors[32],as in metal–ligand or metal–support interactions for homogeneous and heterogeneous catalysis,respectively.Once the exploratory data analysis reveals whether it is possible to highlight positive interactions,and whether one can identify and quantify trends between variables and catalytic performances,a decision must be made—what is the most relevant experimental set to perform next?Computational methods employing mathematics,statistics and artificial intelligence are required for scientists to deal adequately with these three key issues influencing HT experimentation: experimental design,data analysis,and decision making.For over15years,these issues have been addressed in the field of drug discovery,leading to the emergence of a brand new domain of science with its own specialized journals.Section5deals with the application of such screening strategies and their related tools to HT catalyst design,as well as recent developments in the application of quantitative structure–activity relationship(QSAR) to homogeneous and heterogeneous catalysis,with an emphasis on the differences between organic and inorganic compounds in terms of descriptors.Kinetic modeling,on the other hand,reflects the scientist’s insight into the chemical kinetics and,therefore,provides useful information about catalyst behavior.It relates feedstock and operating conditions to reaction rates and corresponding effluent composition,thereby quantifying catalytic performances.Recent kinetic models also contain so-called catalyst descriptors,which specifically account for catalyst properties such as the number of sites and the reactant chemisorption enthalpy.Section4addresses the concepts,recent advances and limitations of kinetic modeling in HT experimentation.An appropriate electronic infrastructure for HT screening is absolutely necessary in order to prevent bottlenecks.Manual entry and cutting-and-pasting of data are to be minimized in order to limit the impact of erroneous entries and slowed-down experiments.Section7addresses these issues,with examples describing and illustrating current technology.Publications,handbooks and other documents available over the Internet,whether free of charge or at a fee,have rendered accessible a great deal of data that could possibly generate knowledge and assist in the decision-making process.That said,the direct capture of data is usually prevented due to the heterogeneity of data,as well as to a lack of standards regarding not just data format but also document format(*.pdf or*.html).The emergence of new technologies,concerted worldwide organizations for electronic standards and new business models appears to be changing this situation.This review does not deal only with catalyst design but also with the optimization of the process conditions due to the strong interplay between catalyst,reactor design and experimental testing conditions.Sections 3.1–3.3address the issues of HT strategies and library design,while Section4explores the benefits of using kinetic and transient approaches for catalyst design.3.Approaches to HT library designThe objectives of a targeted study,such as the discovery of entirely new compounds by exploring large search spaces or the fine optimization of a known catalyst[33,34],have a strong impact on the selection of an appropriate screening strategy and the associated information technology tools.Equipment constraints,synthesis feasibility and screening performances are also important factors to panies or HT departments have developed tailor-made solutions and entire workflows.The issues of HT infrastructure and tool integration as described in[35] will not be discussed here.This section describes the various screening strategies developed in industry and academia,in order from the simplest to the most complex strategies and algorithms, and to some extent from the most massive to the most qualitative screening.3.1.The split&pool methodIn the context of a primary screening aiming to identify hits in a very large search space,the split&pool approach, derived from pharmaceutical methodology,is especially well-suited.It is generally employed in ambitious catalyst discovery programs or when little is known about the target reaction and the class of materials to be studied.Even with a limited number of variables,several hundred samples can easily be obtained thanks to the combinatorial explosion.High analytical speed and overall throughput usually take precedence over the quality or density of information obtained.The split&pool approach enables the generation of every possible combination in a search space.While the generation methodology is quite simple,the major issue,due to its complexity, is the recognition of a molecule in a mixture.For this purpose, many different techniques have been developed to tag molecules, but such techniques cannot be directly applied to inorganic solids. Detailed below are two different tagging strategies,developed by UOP LLC and hte AG,that do allow tagging in the context of inorganic solids.In both strategies,one finds a massive parallel arrangement of micro-reaction chambers containing individual beads,each bead representing one catalyst as a member of a library of solid catalysts.This provides the advantages of easy catalyst handling(unlike the case of powders),very small quantities of metal precursors(typically100µg per catalyst)and a synthesis protocol that can be scaled up.At UOP,catalysts are tagged by using spatially addressable arrays such as microtiter plates(i.e.,96-well plates)[36].Each well contains a single catalyst bead which is indexed by four coordinates,namely the well-plate identity,row and column numbers and split and synthesis step.The combinatorial synthesis consists of a multi-step metal salt impregnation with intermediate drying.Once the metal salt solution is adsorbed onto the beads and dried,rows of beads from a given plate are transferred using a row-sorter to a set of receiving well plates.The sorting algorithm can be set in such a way that the sequence of row-and column-shuffling steps monitors the compositional redundancy of the resulting split–pool library.This process makes it possible for classic,inexpensive laboratory equipment to perform the synthesis of compositionally diverse libraries.The hte AG company has developed fast parallel post-analysis, an alternative to2D addressable layout tagging[37–40].The‘‘split’’step of the split&pool synthesis consists of dividing a few thousand beads into a number of equal portions placed on porcelain dishes. The beads,which are roughly1mm in diameter and are typical catalytic supports,such as alumina or titania,are impregnated with different metallic salt solutions varying by concentration or by metal nature,and then calcined.The beads are then recombined490 D.Farrusseng /Surface Science Reports 63(2008)487–513Fig.1.Split and pool synthesis (a),micro-bead reactor (b)after [39].Table 1Binary composition at the first screening.For each binary system,8different compositions are synthesized using a linear gradientapproach.(‘‘pooled’’)together and are well-mixed via shaking.Typically,the whole process is repeated several times.For example,for five different metal precursors at four different concentrations,the beads are split five times into four different containers (Fig.1).The total number of possible combinations from a mathematical perspective is 45=1024.That said,because the synthesis protocol cannot guarantee that each bead will follow a different path (making the preparation of some identical catalysts possible),it is recommended to start with a greater number of beads,with a ratio of 1.2–1.5with respect to the total theoretical number of combinations.At hte AG,up to 625beads can be tested individually by fast sequential testing methods in a specially-designed array of micro-reactors.The ‘‘hits’’identified are then post-analyzed by micro-X-ray fluorescence (or micro-XRF).In only a few minutes,commercial equipment can quantify the composition of an array of 100samples.The knowledge of the presence or absence of elements and of the range of concentration makes it possible to trace the synthesis path history for the beads.3.2.The hierarchical approachSome erroneous measurements inevitably occur during the primary screening due to the extreme miniaturization and the great number of experiments.Inactive catalysts can appear as ‘‘hits’’(false positives)and active catalysts that should be selected are missed (false negatives).In primary screening,false negatives (which would be missed forever)are far more problematic than are false positives (which would be discarded anyway following the secondary screening).With this fact in mind,Symyx has developed screening strategies to reduce the likelihood of false negatives.Over a two-week period in Symyx laboratories,a hierarchical gradient approach was used with MoVNb patented catalysts for ethane partial oxidation to acetic acid [41].This process led to the discovery of new dopants and to the successful rediscovery of existing catalysts.The primary screening is targeted to identify the best ternary combinations of redox metals from V,Mo,Cr,Mn,Fe,Co,Ni,Cu,Ag,Re,Sn,Sb,Ti and Bi.At the outset,30redox binary systems were investigated,with eight distinct samples synthesizedfor each binary system using a gradient approach consisting of a linear evolution of the composition (Table 1).Of the 30redox binaries (8-point gradients),MoV is by far the most active redox binary,while other active binaries are CrV,MnV,MnCr,CeV,CoCr,CoV,VTi and MoTi.Next,an additional element X was investigated within the MoV system,with X =Mg ,Cr ,Li ,Nb ,Mn ,Co ,Cu ,Fe ,Ni ,Zn ,Zr ,Sb ,Ag ,In or Ce,plus three proprietary dopants.For each ternary,12–15distinct compositions were screened.It was found that Nb,Ni,Sb,and Ce,as well as the three proprietary dopants,result in higher acetic acid productivity.Finally,among the 18ternary MoVX systems,eight of the most promising were tested again with 28different compositions per ternary system.In agreement with the literature,the MoVNb system was identified as very active,while several other metal dopants also produced hits.In summary,as the screening proceeds,the number of com-ponents in the catalytic system increases,formulation complexity increases and higher degrees of interactions are sought in a step-wise manner.The gradient library design approach also permits the efficient management of false negatives and false positives.The testing of similar compositions greatly reduces the risk of missing a hit,while allowing for the easy identification of false positives which afterward are not subjected to further screening.Symyx has demonstrated the value of this screening strategy for various types of catalysis,allowing the determination of the best formulations already reported in the literature and the discovery of new sys-tems [42].For example,the efficiency of Ni–Co–Nb and Ni–Ta–Nb oxide catalysts has successfully been proven for the ethane ox-idative dehydrogenation process at low temperatures [43],while supported-CoCr mixed oxide catalyst systems are proposed for VOC removal [44].Academic laboratories have also applied the gradient strategy.In a primary screening for the partial oxidation of isobutane [45–48],nine elements (V,Fe,Mo,Cr,Ta,Nb,Mn,Sb and Bi)were selected for an initial library design due to the promising partial oxidation properties reported in the literature for the associated oxides.As an alternative to a hierarchical approach,a single library was composed of the nine single oxides (AO x ),D.Farrusseng/Surface Science Reports63(2008)487–513491Fig.2.Emissivity-corrected IR-thermographic images of catalyst library during methanation of CO2at200◦C from[59].of double mixed oxides(A a B b O x)and of ternary mixed oxides (A a B b C c O x).The double mixed oxides consisted of all possible pairs with molar composition(0:1),(0.25:0.75),(0.5:0.5),(0.75:0.25) and(1:0)starting from the nine elements.The ternary mixed oxides consisted of combinations of three elements,always with a(0.33:0.33:0.33)molar composition.Most of the best dehydrogenation catalysts turned out to be Mn and Cr mixed oxides.In accordance with these results,four focused ternary systems–MoVSbO x,MoVFeO x,MoVBiO x and VBiSbO x–were studied in more detail using a dense grinding of the search space. The three elements were allowed to vary between0and100mol% in steps of10mol%,which led to the preparation of66samples per ternary.Other ternaries were investigated elsewhere[49].According to the authors,such composition-spread libraries should allow the identification of any existing local maxima. The best-performing mixed oxides among MoVSbO x,MoVFeO x, MoVBiO x and VBiSbO x were scaled up and tested in a secondary screening.The result was that the optimized composition, Mo10V10Sb80O x,surpassed the best reference catalyst in the literature.Several screening devices have been developed for the mapping of composition-spread libraries.Infrared(IR)thermography is an appropriate choice for the identification of active components in primary screening because,in principle,thousands of samples can be analyzed at the same time[11,50–61].This system records the temperature change arising from the exothermicity or endothermicity of the reaction(Fig.2).In principle,theselectivity Fig.3.Cross-section of the assembled reactor(left)and magnification of reaction chambers(right)from[70].Fig.4.Experimental planning for catalyst design(left).Headers correspond to the element names on the right;M,O,D and S stand for noble Metal,metal Oxides,Dopants and Supports,respectively.Main effects of catalyst compositions on the CO conversion(right),in the absence of H2(a)and in the presence of H2(b).492 D.Farrusseng /Surface Science Reports 63(2008)487–513Fig.5.Blocking structure of 19×19metal binary library (left).Results of 19×19metal binary study (right);synergy was calculated as the difference between the observed TON for the combination minus the sum of the TONs for the individual metals [77].can be measured using an IR focal plane detector [62–65].Other alternatives were developed to overcome selectivity measurement issues such as the use of mass spectrometry (MS)equipped with capillary sampling as shown in [66–70,44,49,71–73].Devices combining IR thermography for rapid hit identification and MS analysis have also been developed [40,74].See also Fig.3.3.3.Design of experiments (DoE)methodology (See also Figs.4and 5)DoE methodology,which involves the simultaneous modifi-cation of variables (usually called factors)and the avoidance of redundant experiments,is widely used in the domain of process engineering.Even though their algorithms are based on simple linear regression,DoE tools can be applied to different objectives that are of particular value in HT experimentation.By means of homogeneous sampling,DoE can be used to efficiently explore a large search space defined by many discrete variables,while guar-anteeing maximal efficiency in terms of the information gleaned from experiments.DoE methodology,when used for screening purposes,quantifies the effect of each individual variable on the targeted properties and identifies the variables relevant to further rounds of screening.On the other hand,when one seeks informa-tion regarding catalytic mechanisms or metal or metal–support synergisms,special DoE design also allows the quantification of in-teractions between variables.Finally,when all relevant variables have been identified,DoE planning is very efficient for the fine op-timization of both catalyst synthesis and process conditions.In this case,the most robust surface responses are generated as empirical models while minimizing the number of experiments.Recent pub-lications illustrate the versatility and power of DoE applied to HT catalyst experimentation.At TU Delft,three sequential DoEs were carried out to find a new one-pot route for the catalytic hydrogenation of acylated cyanohydrins to N -acyl β-amino alcohols [75].Both catalyst formulations and process conditions were varied within the first screening,as shown in Table 2.A selection of 24reactions out of the 320total possible combinations was performed through the use of a D-optimal algorithm.This design is appropriate in view of discarding irrelevant variables for further rounds of optimization.New insights derived from the first design allowed a second one to be carried out using the parameters indicated in Table 3.Variables showing very little impact were discarded.On the other hand,since the nature of the support appeared to bear major importance,a new support,silica,was introduced in the search space.The now considerably reduced parameter space rendered feasible a full-factorial design (i.e.,36combinations),providing accurate information on the main effects of the parameters and especially on the interactions between the parameters.In suchTable 2Definition of the parameter search space for the first screening round.Table 3Definition of the parameter search space for the second screening round.designs,about half the possible number of reactions are typically performed.Finally,a third design was performed in conventional reactors,taking into account other variables such as pressure and temperature.A strategy of sequential hierarchical designs is believed to be better than a single large one,because the information obtained from one design is used to improve the next.If one large DoE design had been chosen,many unnecessary reactions would have been performed.Preliminary designs (typically fewer than 25%of the possible reactions)are sufficient to allow differentiation between significant and insignificant parameters,and are therefore well-suited to reduce the search space in the early stages of the research effort.The search for selective CO oxidation catalysts for H 2purifica-tion applications has also been a context for using a very similar hi-erarchical strategy using a D-optimal design algorithm for primary screening [76].An a priori selection of elements and of combinato-rial rules for mixing them and generating multi-component cata-lysts was performed according to literature data and pre-existing knowledge.Four groups of elements were considered:noble met-als (Pt,Pd,Ru,Rh and Au),oxides (transition metal oxides of Cr,Co,Mn,La,Sm and Mo),dopants (alkali or earth alkali Li,Cs and Ca)and supports (Al 2O 3,CeO 2,ZrO 2,ZnO and C).One of the a priori rules established was that all catalysts were to be composed of one sup-port and two noble metals and,optionally,of one transition metal and one dopant.The weight percentages of noble metal,as well as transition metal and dopant (when present),were fixed at 0.5%,20%and 1%,respectively.The choice to employ two distinct noble metals per catalyst was based on the assumption that alloys may。
Oswald ripening
Ostwald ripeningBasic schematic of the Ostwald ripening processOstwald ripening is an observed phenomenon in solid solutions or liquid sols that describes the change of an inhomogeneous structure over time, i.e., small crystals or sol particles dissolve, and redeposit onto larger crystals or sol particles.[1]Dissolution of small crystals or sol particles and the redeposition of the dissolved species on the surfaces of larger crystals or sol particles was first described by Wilhelm Ostwald in 1896.[2][3] Ostwald ripening is generally found in water-in-oil emulsions, while flocculation is found in oil-in-water emulsions.[4] MechanismThis thermodynamically-driven spontaneous process occurs because larger particles are more energetically favored than smaller particles.[5] This stems from the fact that molecules on the surface of a particle are energetically less stable than the ones in the interior.Cubic crystal structure (sodium chloride)Consider a cubic crystal of atoms: all the atoms inside are bonded to 6 neighbors and are quite stable, but atoms on the surface are only bonded to 5 neighbors or fewer, which makes these surface atoms less stable. Large particles are more energetically favorable since, continuing with this example, more atoms are bonded to 6 neighbors and fewer atoms are at the unfavorable surface. As the system tries to lower its overall energy, molecules on the surface of a small particle (energetically unfavorable, with only 3 or 4 or 5 bonded neighbors) will tend to detach from the particle, as per the Kelvin equation, and diffuse into the solution. When all small particles do this, it increases the concentration of free molecules in solution. When the free molecules in solution are supersaturated, the free molecules have a tendencyto condense on the surface of larger particles.[5] Therefore, all smaller particles shrink, while larger particles grow, and overall the average size will increase. As time tends to infinity, the entire population of particles becomes one large spherical particle to minimize the total surface area.In 1958, Lifshitz and Slyozov [6] performed a mathematical investigation of Ostwald ripening in the case where diffusion of material is the slowest process. They began by stating how a single particle grows in asolution. This equation describes where the boundary is between small, shrinking particles and large, growing particles. They finally conclude that the average radius of the particles ⟨R⟩, grows as follows:where= a verage radius of all the particles= p article surface tension or surface energy= s olubility of the particle material= m olar volume of the particle material= d iffusion coefficient of the particle material= i deal gas constant= a bsolute temperature and= t ime.Note that the quantity ⟨R⟩3 is different from ⟨R3⟩, and only the latter one can be used to calculate average volume, and that the statement that ⟨R⟩ goes as t1/3 relies on ⟨R⟩0 being zero; but because nucleation is a separate process from growth, this places ⟨R⟩0 outside the bounds of validity of the equation. In contexts where the actual value of ⟨R⟩0 is irrelevant, an approach that respects the meanings of all terms is to take the time derivative of the equation to eliminate ⟨R⟩0 and t. Another such approach is to changethe ⟨R⟩0 to ⟨R⟩i with the initial timei having a positive value.Also contained in the Lifshitz and Slyozov derivation is an equation for the size distribution function f(R, t) of particles. For convenience, the radius of particles is divided by the average radius to form a new variable, ρ = R(⟨R⟩)-1.Three years after that Lifshitz and Slyozov published their findings (in Russian, 1958), Carl Wagner performed his own mathematical investigation of Ostwald ripening,[7] examining both systemswhere diffusion was slow and also where attachment and detachment at the particle surface was slow. Although his calculations and approach were different, Wagner came to the same conclusions as Lifshitz and Slyozov for slow-diffusion systems. This duplicate derivation went unnoticed for years because the two scientific papers were published on opposite sides of the Iron Curtain in 1961.[citation needed] It was not until 1975 that Kahlweit addressed the fact that the theories were identical[8] and combined them into the Lifshitz-Slyozov-Wagner or LSW Theory of Ostwald ripening. Many experiments and simulations have shown LSW theory to be robust and accurate. Even some systems that undergo spinodal decomposition have been shown to quantitatively obey LSW theory after initial stages of growth.[9] Wagner derived that when attachment and detachment of molecules is slower than diffusion, then the growth rate becomeswhere k s is the reaction rate constant of attachment with units of length per time. Since the average radius is usually something that can be measured in experiments, it is fairly easy to tell if a system is obeying the slow-diffusion equation or the slow-attachment equation. If the experimental data obeysneither equation, then it is likely that another mechanism is taking place and Ostwald ripening is not occurring.Although LSW theory and Ostwald ripening were intended for solids ripening in a fluid, Ostwald ripening is also observed in liquid-liquid systems, for example, in an oil-in-water emulsion polymerization.[4] In this case, Ostwald ripening causes the diffusion of monomers (i.e. individual molecules or atoms) from smaller droplets to larger droplets due to greater solubility of the single monomer molecules in the larger monomer droplets. The rate of this diffusion process is linked to the solubility of the monomer in the continuous (water) phase of the emulsion. This can lead to the destabilization of emulsions (for example, by creaming and sedimentation).[10]Specific examples。
211050371_正负压一体式无空气X_射线光电子能谱原位转移仓的开发及研制
第 29 卷第 1 期分析测试技术与仪器Volume 29 Number 1 2023年3月ANALYSIS AND TESTING TECHNOLOGY AND INSTRUMENTS Mar. 2023大型仪器功能开发(30 ~ 36)正负压一体式无空气X射线光电子能谱原位转移仓的开发及研制章小余,赵志娟,袁 震,刘 芬(中国科学院化学研究所,北京 100190)摘要:针对空气敏感材料的表面分析,为了获得更加真实的表面组成与结构信息,需要提供一个可以保护样品从制备完成到分析表征过程中不接触大气环境的装置. 通过使用O圈密封和单向密封柱,提出一种简便且有效的设计概念,自主研制了正负压一体式无空气X射线光电子能谱(XPS)原位转移仓,用于空气敏感材料的XPS测试,利用单向密封柱实现不同工作需求下正负压两种模式的任意切换. 通过对空气敏感的金属Li片和CuCl粉末进行XPS分析表明,采用XPS原位转移仓正压和负压模式均可有效避免样品表面接触空气,保证测试结果准确可靠,而且采用正压密封方式转移样品可以提供更长的密封时效性. 研制的原位转移仓具有设计小巧、操作简便、成本低、密封效果好的特点,适合给有需求的用户开放使用.关键词:空气敏感;X射线光电子能谱;原位转移;正负压一体式中图分类号:O657; O641; TH842 文献标志码:B 文章编号:1006-3757(2023)01-0030-07 DOI:10.16495/j.1006-3757.2023.01.005Development and Research of Inert-Gas/Vacuum Sealing Air-Free In-Situ Transfer Module of X-Ray Photoelectron SpectroscopyZHANG Xiaoyu, ZHAO Zhijuan, YUAN Zhen, LIU Fen(Institute of Chemistry Chinese Academy of Sciences, Beijing 100190, China)Abstract:For the surface analysis of air sensitive materials, and from the sample preparation to characterization, it is necessary to provide a device that can protect samples from exposing to the atmosphere environment so as to obtain accurate and impactful data of the surface chemistry. Through the use of O-ring and one-way sealing, a simple and effective design concept has been demonstrated, and an inert-gas/vacuum sealing air-free X-ray photoelectron spectroscopic (XPS) in-situ transfer module has been developed to realize the XPS analysis of air sensitive materials. The design of one-way sealing was achieved conveniently by switching between inert-gas and vacuum sealing modes in face of different working requirements. The XPS analysis of air-sensitive metal Li sheets and CuCl powders showed that both the sealing modes (an inert-gas/vacuum sealing) of the XPS in-situ transfer module can effectively avoid air contact on the sample surface, and consequently, can ensure the accuracy and reliability of XPS data. Furthmore, the inert gas sealing mode can keep the sample air-free for a longer time. The homemade XPS in-situ transfer module in this work is characterized by a compact design, convenient operation, low cost and effective sealing, which is suitable for the open access to the users who need it.收稿日期:2022−12−07; 修订日期:2023−01−17.基金项目:中国科学院化学研究所仪器孵化项目[Instrument and Device Functional Developing Project of Institute of Chemistry Chinese Academy of Sciences]作者简介:章小余(1986−),女,硕士,工程师,主要研究方向为电子能谱技术及材料表面分析,E-mail:xyiuzhang@ .Key words:air-sensitive;X-ray photoelectron spectroscopy;in-situ transfer;inert-gas/vacuum sealingX射线光电子能谱(XPS)是一种表面灵敏的分析技术,通常用于固体材料表面元素组成和化学态分析[1]. 作为表面分析领域中最有效的方法之一,XPS广泛应用于纳米科学、微电子学、吸附与催化、环境科学、半导体、冶金和材料科学、能源电池及生物医学等诸多领域[2-3]. 其中在催化和能源电池材料分析中,有一些样品比较特殊,比如碱金属电池[4-6]、负载型纳米金属催化剂[7-8]和钙钛矿材料[9]对空气非常敏感,其表面形态和化学组成接触空气后会迅速发生改变,直接影响采集数据的准确性和有效性,因此这类样品的表面分析测试具有一定难度. 目前,常规的光电子能谱仪制样转移过程通常是在大气环境中,将样品固定在标准样品台上,随后放入仪器进样室内抽真空至1×10−6 Pa,再转入分析室内进行测试. 这种制备和进样方式无法避免样品接触大气环境,对于空气敏感材料,其表面很容易与水、氧发生化学反应,导致无法获得材料表面真实的结构信息.为了保证样品表面状态在转移至能谱仪内的过程中不受大气环境影响,研究人员采用了各种技术来保持样品转移过程中隔绝空气. 比如前处理及反应装置与电子能谱仪腔室间真空传输[10-12]、外接手套箱 [13-14]、商用转移仓[15-16]、真空蒸镀惰性金属比如Al层(1.5~6 nm)[17]等. 尽管上述技术手段有效,但也存在一些缺点,例如配套装置体积巨大、试验过程不易操作、投入成本高等,这都不利于在普通实验室内广泛应用. 而一些电子能谱仪器制造商根据自身仪器的特点也研发出了相应配套的商用真空传递仓,例如Thermofisher公司研发的一种XPS 真空转移仓,转移过程中样品处于微正压密封状态,但其价格昂贵,体积较大,转移过程必须通过手套箱大过渡舱辅助,导致传递效率低,单次需消耗至少10 L高纯氩气,因此购置使用者较少,利用率低.另外有一些国内公司也研发了类似的商品化气体保护原位传递仓,采用微正压方式密封转移样品,但需要在能谱仪器进样室舱门的法兰上外接磁耦合机械旋转推拉杆,其操作复杂且放置样品的有效区域小,单次仅可放置尺寸为3 mm×3 mm的样品3~4个,进样和测试效率较低. 因此,从2016年起本实验团队开始自主研制XPS原位样品转移装置[18],经过结构与性能的迭代优化[19],最终研制出一种正负压一体式无空气XPS原位转移仓[20](本文简称XPS原位转移仓),具有结构小巧、操作便捷、成本低、密封效果好、正压和负压密封两种模式转移样品的特点. 为验证装置的密封时效性能,本工作选取两种典型的空气敏感材料进行测试,一种是金属Li材料,其化学性质非常活泼,遇空气后表面迅速与空气中的O2、N2、S等反应导致表面化学状态改变. 另一种是无水CuCl粉末,其在空气中放置短时间内易发生水解和氧化. 试验结果表明,该XPS 原位转移仓对不同类型的空气敏感样品的无空气转移均可以提供更便捷有效的密封保护. 目前,XPS原位转移仓已在多个科研单位的实验室推广使用,支撑应用涉及吸附与催化、能源环境等研究领域.1 试验部分1.1 XPS原位转移仓的研制基于本实验室ESCALAB 250Xi型多功能光电子能谱仪器(Thermofisher 公司)的特点,研究人员设计了XPS原位转移仓. 为兼顾各个部件强度、精度与轻量化的要求,所有部件均采用钛合金材料.该装置从整体结构上分为样品台、密封罩和紧固挡板三个部件,如图1(a)~(c)所示. 在密封罩内部通过单向密封设计[图1(e)]使得XPS原位转移仓实现正负压一体,实际操作中可通过调节密封罩上的螺帽完成两种模式任意切换. 同时,从图1(e)中可以直观看到,密封罩与样品台之间通过O圈密封,利用带有螺钉的紧固挡板将二者紧密固定. 此外,为确保样品台与密封罩对接方位正确,本设计使用定向槽定位样品台与密封罩位置,保证XPS原位转移仓顺利传接到仪器进样室.XPS原位转移仓使用的具体流程:在手套箱中将空气敏感样品粘贴至样品台上,利用紧固挡板使样品台和密封罩固定在一起,通过调节密封罩上的螺帽将样品所在区域密封为正压惰性气氛(压强为300 Pa、环境气氛与手套箱内相同)或者负压真空状态,其整体装配实物图如图1(d)所示. 该转移仓结构小巧,整体尺寸仅52 mm×58 mm×60 mm,可直接放入手套箱小过渡舱传递. 由于转移仓尺寸小,其第 1 期章小余,等:正负压一体式无空气X射线光电子能谱原位转移仓的开发及研制31原料成本大大缩减,整体造价不高. 转移仓送至能谱仪进样室后,配合样品停放台与进样杆的同时双向对接,将转移仓整体固定在进样室内,如图1(f )所示. 此时关闭进样室舱门开始抽真空,当样品台与密封罩内外压强平衡后密封罩自动解除真空密封,但仍然处于O 圈密闭状态. 等待进样室真空抽至1×10−4Pa 后,使用能谱仪进样室的样品停放台摘除脱离的密封罩[如图1(g )所示],待真空抽至1×10−6Pa ,即可将样品送入分析室进行XPS 测试.整个试验过程操作便捷,实现了样品从手套箱转移至能谱仪内不接触大气环境.1.2 试验过程1.2.1 样品准备及转移试验所用手套箱是布劳恩惰性气体系统(上海)有限公司生产,型号为MB200MOD (1500/780)NAC ;金属Li 片购自中能锂业,纯度99.9%;CuCl 购自ALFA 公司,纯度99.999%.金属Li 片的制备及转移:将XPS 原位转移仓整体通过手套箱过渡舱送入手套箱中,剪取金属Li 片用双面胶带固定于样品台上,分别采用正压、负压两种密封模式将XPS 原位转移仓整体从手套箱中取出,分别在空气中放置0、2、4、8、18、24、48、72 h 后送入能谱仪内,进行XPS 测试.CuCl 粉末的制备及转移:在手套箱中将CuCl 粉末压片[21],使用上述同样的制备方法,将XPS 原位转移仓整体在空气中分别放置0、7、24、72 h 后送入能谱仪内,进行XPS 测试.1.2.2 样品转移方式介绍样品在手套箱中粘贴完成后,分别采用三种方式将其送入能谱仪. 第一种方式是在手套箱内使用标准样品台粘贴样品,将其装入自封袋密封,待能谱仪进样室舱门打开后,即刻打开封口袋送入仪器中开始抽真空等待测试,整个转移过程中样品暴露空气约15 s. 第二种方式是使用XPS 原位转移仓负压密封模式转移样品,具体操作步骤:利用紧固挡板将样品台和密封罩固定在一起,逆时针(OPEN )旋动螺帽至顶部,放入手套箱过渡舱并将其抽为真空,此过程中样品所在区域也抽至负压. 取出整体装置后再顺时针(CLOSE )旋动螺帽至底部,将样品所在区域进一步锁死密封. 样品在负压环境中转移至XPS 实验室,拆卸掉紧固挡板,随即送入能谱仪进样室内. 第三种方式是使用XPS 原位转移仓正压密封模式转移样品,具体操作步骤:利用紧固挡板将样品台和密封罩固定在一起,顺时针(CLOSE )旋螺帽抽气管限位板单向密封柱密封罩主体O 圈样品台紧固挡板(e) 密封罩对接停放台机械手样品台对接进样杆(a)(b)(c)(d)(g)图1 正负压一体式无空气XPS 原位转移仓系统装置(a )样品台,(b )密封罩,(c )紧固挡板,(d )整体装配实物图,(e )整体装置分解示意图,(f )样品台与密封罩在进样室内对接完成,(g )样品台与密封罩在进样室内分离Fig. 1 System device of inert-gas/vacuum sealing air-free XPS in-situ transfer module32分析测试技术与仪器第 29 卷动螺帽至底部,此时样品所在区域密封为正压惰性气氛. 直至样品转移至XPS 实验室,再使用配套真空抽气系统(如图2所示),通过抽气管将样品所在区域迅速抽为负压,拆卸掉紧固挡板,随即送入能谱仪进样室内.图2 能谱仪实验室内配套真空抽气系统Fig. 2 Vacuum pumping system in XPSlaboratory1.2.3 XPS 分析测试试验所用仪器为Thermo Fisher Scientific 公司的ESCALAB 250Xi 型多功能X 射线光电子能谱仪,仪器分析室基础真空为1×10−7Pa ,X 射线激发源为单色化Al 靶(Alk α,1 486.6 eV ),功率150 W ,高分辨谱图在30 eV 的通能及0.05 eV 的步长等测试条件下获得,并以烃类碳C 1s 为284.8 eV 的结合能为能量标准进行荷电校正.2 结果与讨论2.1 测试结果分析为了验证XPS 原位转移仓的密封性能,本文做了一系列的对照试验,选取空气敏感的金属Li 片和CuCl 粉末样品进行XPS 测试,分别采用上述三种方式转移样品,并考察了XPS 原位转移仓密封状态下在空气中放置不同时间后对样品测试结果的影响.2.1.1 负压密封模式下XPS 原位转移仓对金属Li片的密封时效性验证将金属Li 片通过两种(标准和负压密封)方式转移并在空气中放置不同时间,对这一系列样品进行XPS 测试,Li 1s 和C 1s 高分辨谱图结果如图3(a )(b )所示,试验所测得的Li 1s 半峰宽值如表1所列. 根据XPS 结果分析,金属Li 片采用标准样品台进样(封口袋密封),短暂暴露空气约15 s ,此时Li 1s 的半峰宽为1.62 eV. 而采用XPS 原位转移仓负压密封模式转移样品时,装置整体放置空气18 h 内,Li 1s 的半峰宽基本保持为(1.35±0.03) eV. 放置空气24 h 后,Li 1s 的半峰宽增加到与暴露空气15 s 的金属Li 片一样,说明此时原位转移仓的密封性能衰减,金属Li 片与渗入内部的空气发生反应生成新物质导致Li 1s 半峰宽变宽. 由图3(b )中C 1s 高分辨谱图分析,结合能位于284.82 eV 的峰归属为C-C/污染C ,位于286.23 eV 的峰归属为C-OH/C-O-CBinding energy/eVI n t e n s i t y /a .u .Li 1s半峰宽增大暴露 15 s密封放置 24 h 密封放置 18 h 密封放置 8 h 密封放置 4 h 密封放置 0 h6058565452Binding energy/eVI n t e n s i t y /a .u .C 1s(a)(b)暴露 1 min 暴露 15 s 密封放置 24 h 密封放置 18 h 密封放置 0 h292290288284282286280图3 金属Li 片通过两种(标准和负压密封)方式转移并在空气中放置不同时间的(a )Li 1s 和(b )C 1s 高分辨谱图Fig. 3 High-resolution spectra of (a) Li 1s and (b) C 1s of Li sheet samples transferred by two methods (standard andvacuum sealings) and placed in air for different times第 1 期章小余,等:正负压一体式无空气X 射线光电子能谱原位转移仓的开发及研制33键,位于288.61~289.72 eV的峰归属为HCO3−/CO32−中的C[22]. 我们从C 1s的XPS谱图可以直观的看到,与空气短暂接触后,样品表面瞬间生成新的结构,随着暴露时间增加到1 min,副反应产物大量增加(HCO3−/CO32−). 而XPS原位转移仓负压密封模式下在空气中放置18 h内,C结构基本不变,在空气中放置24 h后,C结构只有微小变化. 因此根据试验结果分析,对于空气极其敏感的材料,在负压密封模式下,建议XPS原位转移仓在空气中放置时间不要超过18 h. 这种模式适合对空气极其敏感样品的短距离转移.表 1 通过两种(标准和负压密封)方式转移并在空气中放置不同时间的Li 1s的半峰宽Table 1 Full width at half maxima (FWHM) of Li 1stransferred by two methods (standard and vacuum sealings) and placed in air for different times样品说明进样方式半峰宽/eV密封放置0 h XPS原位转移仓负压密封模式转移1.38密封放置2 h同上 1.39密封放置4 h同上 1.36密封放置8 h同上 1.32密封放置18 h同上 1.32密封放置24 h同上 1.62暴露15 s标准样品台进样(封口袋密封)1.622.1.2 正压密封模式下原位转移仓对金属Li片的密封时效性验证将金属Li片通过两种(标准和正压密封)方式转移并在空气中放置不同时间,对这一系列样品进行XPS测试,Li 1s高分辨谱图结果如图4所示,所测得的Li 1s半峰宽值如表2所列. 根据XPS结果分析,XPS原位转移仓正压密封后,在空气中放置72 h内,Li 1s半峰宽基本保持为(1.38±0.04) eV,说明有明显的密封效果,金属Li片仍然保持原有化学状态. 所以对于空气极其敏感的材料,在正压密封模式下,可至少在72 h内保持样品表面不发生化学态变化. 这种模式适合长时间远距离(可全国范围内)转移空气敏感样品.2.1.3 负压密封模式下XPS原位转移仓对空气敏感样品CuCl的密封时效性验证除了金属Li片样品,本文还继续考察XPS原位转移仓对空气敏感样品CuCl的密封时效性. 图5为CuCl粉末通过两种(标准和负压密封)方式转移并在空气中放置不同时间的Cu 2p高分辨谱图. XPS谱图中结合能[22]位于932.32 eV的峰归属为Cu+的Cu 2p3/2,位于935.25 eV的峰归属为Cu2+的Cu 2p3/2,此外,XPS谱图中位于940.00~947.50 eV 处的峰为Cu2+的震激伴峰,这些震激伴峰被认为是表 2 通过两种(标准和正压密封)方式转移并在空气中放置不同时间的Li 1s的半峰宽Table 2 FWHM of Li 1s transferred by two methods(standard and inert gas sealings) and placed in air fordifferent times样品说明进样方式半峰宽/eV 密封放置0 h XPS原位转移仓正压密封模式转移1.42密封放置2 h同上 1.35密封放置4 h同上 1.35密封放置8 h同上 1.34密封放置18 h同上 1.38密封放置24 h同上 1.39密封放置48 h同上 1.42密封放置72 h同上 1.38暴露15 s标准样品台进样(封口袋密封)1.62Binding energy/eVIntensity/a.u.Li 1s半峰宽比正压密封的宽半峰宽=1.62 eV半峰宽=1.38 eV暴露 15 s密封放置 72 h密封放置 48 h密封放置 24 h密封放置 18 h密封放置 0 h605856545250图4 金属Li片通过两种(标准和正压密封)方式转移并在空气中放置不同时间的Li 1s高分辨谱图Fig. 4 High-resolution spectra of Li 1s on Li sheet samples transferred by two methods (standard and inert gas sealings) and placed in air for different times34分析测试技术与仪器第 29 卷价壳层电子向激发态跃迁的终态效应所产生[23],而在Cu +和Cu 0中则观察不到.根据XPS 结果分析,CuCl 在XPS 原位转移仓保护(负压密封)下,即使放置空气中72 h ,测得的Cu 2p 高分辨能谱图显示只有Cu +存在,说明CuCl 并未被氧化. 若无XPS 原位转移仓保护,CuCl 粉末放置空气中3 min 就发生了比较明显的氧化,从测得的Cu 2p 高分辨能谱图能够直观的看到Cu 2+及其震激伴峰的存在,并且随着放置时间增加到40 min ,其氧化程度也大大增加. 因此,对于空气敏感的无机材料、纳米催化剂和钙钛矿材料等,采用负压密封模式转移就可至少在72 h 内保持样品表面不发生化学态变化.3 结论本工作中自主研制的正负压一体式无空气XPS原位转移仓在空气敏感样品转移过程中可以有效隔绝空气,从而获得样品最真实的表面化学结构.试验者可根据样品情况和实验室条件选择转移模式,并在密封有效时间内将样品从实验室转移至能谱仪中完成测试. 综上所述,该XPS 原位转移仓是一种设计小巧、操作简便、密封性能优异、成本较低的样品无水无氧转移装置,因此非常适合广泛开放给有需求的试验者使用. 在原位和准原位表征技术被广泛用于助力新材料发展的现阶段,希望该设计理念能对仪器功能的开发和更多准原位表征测试的扩展提供一些启示.参考文献:黄惠忠. 论表面分析及其在材料研究中的应用[M ].北京: 科学技术文献出版社, 2002: 16-18.[ 1 ]杨文超, 刘殿方, 高欣, 等. X 射线光电子能谱应用综述[J ]. 中国口岸科学技术,2022,4(2):30-37.[YANG Wenchao, LIU Dianfang, GAO Xin, et al.TheapplicationofX -rayphotoelectronspectroscopy [J ]. China Port Science and Technology ,2022,4 (2):30-37.][ 2 ]郭沁林. X 射线光电子能谱[J ]. 物理,2007,36(5):405-410. [GUO Qinlin. X -ray photoelectron spectro-scopy [J ]. Physics ,2007,36 (5):405-410.][ 3 ]Malmgren S, Ciosek K, Lindblad R, et al. Con-sequences of air exposure on the lithiated graphite SEI [J ]. Electrochimica Acta ,2013,105 :83-91.[ 4 ]Zhang Y H, Chen S M, Chen Y, et al. Functional poly-ethylene glycol-based solid electrolytes with enhanced interfacial compatibility for room-temperature lithium metal batteries [J ]. Materials Chemistry Frontiers ,2021,5 (9):3681-3691.[ 5 ]周逸凡, 杨慕紫, 佘峰权, 等. X 射线光电子能谱在固态锂离子电池界面研究中的应用[J ]. 物理学报,2021,70(17):178801. [ZHOU Yifan, YANG Muzi,SHE Fengquan, et al. Application of X -ray photoelec-tron spectroscopy to study interfaces for solid-state lithium ion battery [J ]. 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Characterization[ 10 ]Binding energy/eVI n t e n s i t y /a .u .Cu 2pCu +Cu 2+暴露 3 min暴露 40 min 密封放置 7 h 密封放置 72 h 密封放置 24 h密封放置 0 h960950945935925955940930920图5 CuCl 粉末通过两种(标准和负压密封)方式转移并在空气中放置不同时间的Cu 2p 高分辨谱图Fig. 5 High-resolution spectra of Cu 2p on CuCl powder samples transferred by two methods (standard and vacuumsealings) and placed in air for different times第 1 期章小余,等:正负压一体式无空气X 射线光电子能谱原位转移仓的开发及研制35of surface processes at the Ni-based catalyst during the methanation of biomass-derived synthesis gas: X -ray photoelectron spectroscopy (XPS)[J ]. Applied Cata-lysis A:General ,2007,329 :68-78.Rutkowski M M, McNicholas K M, Zeng Z Q, et al.Design of an ultrahigh vacuum transfer mechanism to interconnect an oxide molecular beam epitaxy growth chamber and an X -ray photoemission spectroscopy analysis system [J ]. Review of Scientific Instruments ,2013,84 (6):065105.[ 11 ]伊晓东, 郭建平, 孙海珍, 等. X 射线光电子能谱仪样品前处理装置的设计及应用[J ]. 分析仪器,2008(5):8-11. [YI Xiaodong, GUO Jianping, SUN Haizhen, et al. Design of a sample pretreatment device for X -ray photoelectron spectrometer [J ]. Analytical Instrumentation ,2008 (5):8-11.][ 12 ]Aurbach D, Weissman I, Schechter A, et al. X -ray pho-toelectron spectroscopy studies of lithium surfaces pre-pared in several important electrolyte solutions. A comparison with previous studies by Fourier trans-form infrared spectroscopy [J ]. Langmuir ,1996,12(16):3991-4007.[ 13 ]Światowska-Mrowiecka J, Maurice V, Zanna S, et al.XPS study of Li ion intercalation in V 2O 5 thin films prepared by thermal oxidation of vanadium metal [J ].Electrochimica Acta ,2007,52 (18):5644-5653.[ 14 ]Weingarth D, Foelske-Schmitz A, Wokaun A, et al. Insitu electrochemical XPS study of the Pt/[BF 4]system [J ]. Electrochemistry Communications ,2011,13 (6):619-622.[ 15 ]Schneider J D, Agocs D B, Prieto A L. Design of asample transfer holder to enable air-free X -ray photo-electron spectroscopy [J ]. 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Surface mining - Wikipedia, the free encyclopedia
Coal strip mine in Wyoming From Wikipedia, the free encyclopediaSurface mining , including strip mining ,open-pit mining and mountaintop removalmining, is a broad category of mining inwhich soil and rock overlying the mineraldeposit (the overburden) are removed. Incontrast to underground mining, in which theoverlying rock is left in place, and themineral removed through shafts or tunnels.Surface mining began in the mid-sixteenthcentury [1] and is practiced throughout theworld, although the majority of surfacemining occurs in North America.[2] It gainedpopularity throughout the 20th century, andis now the predominant form of mining incoal beds such as those in Appalachia and America's Midwest.In most forms of surface mining, heavy equipment, such as earthmovers, first remove theoverburden. Next, huge machines, such as dragline excavators or Bucket wheel excavators,extract the mineral.1Types1.1Strip mining1.2Open-pit mining1.3Mountaintop removal1.4Dredging1.5Highwall mining2Environmental and health issues2.1Human health2.2Environmental impact3In popular culture4See also5References6External linksThere are five main forms of surface mining, detailed below.Strip mining"Strip mining" is the practice of mining a seam of mineral, by first removing a long strip of overlyingsoil and rock (the overburden). It is most commonly used to mine coal and lignite (brown coal).Strip mining is only practical when the ore body to be excavated is relatively near the surface. ThisThe Bagger 288 is a bucket-wheel excavatorused in strip mining.The El Chino mine located near Silver City, New Mexico is an open-pit copper mine.type of mining uses some of the largest machineson earth, including bucket-wheel excavators which can move as much as 12,000 cubic meters of earthper hour.There are two forms of strip mining. The more common method is "area stripping", which is used on fairly flat terrain, to extract deposits over a largearea. As each long strip is excavated, theoverburden is placed in the excavation produced by the previous strip."Contour stripping" involves removing the overburden above the mineral seam near the outcrop inhilly terrain, where the mineral outcrop usually follows the contour of the land. Contour stripping isoften followed by auger mining into the hillside, to remove more of the mineral. This methodcommonly leaves behind terraces in mountainsides.Strip mining at Garzweiler, Germany. The lignite being extracted is at left, the removed overburden beingplaced at right. Note that it is a largely flat mine for a horizontal mineral.Open-pit mining"Open-pit mining" refers to a method of extracting rock orminerals from the earth through their removal from an open pitor borrow. Although open-pit mining is sometimes mistakenlyreferred to as "strip mining", the two methods are different (seeabove).Mountaintop removal"Mountaintop removal mining" (MTR) is a form of coal miningthat uses explosives to blast "overburden" off the top of some mountains. Excess mining waste or "overburden" is dumped by large trucks into fills in nearby hollow or valley fills. MTR involves the mass restructuring of earth in order to reach thecoal seam as deep as 400 feet (120 m) below the surface.Mountaintop removal replaces the original steep landscape with a much flatter topography.Economic development attempts on reclaimed mine sites include prisons such the Big SandyFederal Penitentiary in Martin County, Kentucky, small town airports, golf courses such as TwistedGun in Mingo County, West Virginia and Stonecrest Golf Course in Floyd County, Kentucky, as wellas industrial scrubber sludge disposal sites, solid waste landfills, trailer parks, explosivemanufacturers, and storage rental lockers.[3]The technique has been used increasingly in recent years in the Appalachian coal fields of West Virginia, Kentucky, Virginia and Tennessee in the United States. The profound changes in topography and disturbance of pre-existing ecosystems have made mountaintop removal highly controversial.Advocates of mountaintop removal point out that once the areas are reclaimed as mandated by law, the technique provides premium flat land suitable for many uses in a region where flat land is at a premium. They also maintain that the new growth on reclaimed mountaintop mined areas is better able to support populations of game animals.[4]Critics contend that mountaintop removal is a disastrous practice that benefits a small number of corporations at the expense of local communities and the environment. A U.S. Environmental Protection Agency (EPA) environmental impact statement finds that streams near valley fills sometimes may contain higher levels of minerals in the water and decreased aquatic biodiversity.[5] The statement also estimates that 724 miles (1,165 km) of Appalachian streams were buried by valley fills from 1985 to 2001.Blasting at a mountaintop removal mine expels dust and fly-rock into the air, which can then disturb or settle onto private property nearby. This dust may contain sulfur compounds, which some claim corrode structures and tombstones and is a health hazard.[6]Although MTR sites are required to be reclaimed after mining is complete, reclamation has traditionally focused on stabilizing rock and controlling erosion, but not always on reforesting the area.[7] Quick-growing, non-native grasses, planted to quickly provide vegetation on a site, compete with tree seedlings, and trees have difficulty establishing root systems in compacted backfill.[5] Consequently, biodiversity suffers in a region of the United States with numerous endemic species.[8]Erosion also increases, which can intensify flooding. In the Eastern United States, the Appalachian Regional Reforestation Initiative works to promote the use of trees in mining reclamation.[9]Dredging"Dredging" is a method often used to bring up underwater mineral deposits. Although dredging is usually employed to clear or enlarge waterways for boats, it can also recover significant amounts of underwater minerals relatively efficiently and cheaply. Used widely in oil refining.Highwall miningHighwall mining is another form of surface mining that evolved from auger mining. In Highwall mining, the coal seam is penetrated by a continuous miner propelled by a hydraulic Pushbeam Transfer Mechanism (PTM). A typical cycle includes sumping (launch-pushing forward) and shearing (raising and lowering the cutterhead boom to cut the entire height of the coal seam). As the coal recovery cycle continues, the cutterhead is progressively launched into the coal seam for 19.72 feet (6.01 m). Then, the Pushbeam Transfer Mechanism (PTM) automatically inserts a19.72-foot (6.01 m) long rectangular Pushbeam (Screw-Conveyor Segment) into the center section of the machine between the Powerhead and the cutterhead. The Pushbeam system can penetrate nearly 1,000 feet (300 m) into the coal seam. One patented Highwall mining systems use augers enclosed inside the Pushbeam that prevent the mined coal from being contaminated by rock debris during the conveyance process. Using a video imaging and/or a gamma ray sensor and/or other Geo-Radar systems like a coal-rock interface detection sensor (CID), the operator can see ahead projection of the seam-rock interface and guide the continuous miner's progress. Highwall mining can produce thousands of tons of coal in contour-strip operations with narrow benches, previously mined areas, trench mine applications and steep-dip seams with controlled water-inflow pumpsystem and/or a gas (inert) venting system.Recovery is much better than Augering, but the mapping of areas that have been developed by a Highwall miner are not mapped as rigorously as deep mined areas. Very little soil is displaced in contrast with mountain top removal; however a large amount of capital is required to operate and own a Highwall miner. But then this Highwall mining system is the innovative roadmap future potential and stay or being better competitive in the area of environmental friendly nonmountain-top (overburden) removal operated by only 4 crew members.Mapping of the outcrop as well as core hole data and samples taken during the bench making process are taken into account to best project the panels that the Highwall miner will cut. Obstacles that could be potentially damaged by subsidence and the natural contour of the Highwall are taken into account, and a surveyor points the Highwall miner in a line (Theoretical SurveyPlot-Line) mostly perpendicular to the Highwall. Parallel lines represent the drive cut into the mountain (up to 1,000 feet (300 m) deep), without heading or corrective steering actuation on a navigation Azimuth during mining results in missing a portion of the coal seam and is a potential danger of cutting in pillars from previous mined drives due to horizontal drift (Roll) of the Pushbeam-Cuttermodule string. Recently Highwall miners have penetrated more than 1050 feet into the coal seam, and today's models are capable of going farther, with the support of gyro navigation and not limited anymore by the amount of cable stored on the machine. The maximum depth would be determined by the stress of further penetration and associated specific-power draw, ("Torsion and Tension" in Screw-Transporters String) but today's optimized Screw-Transporters Conveying Embodiments (called: Pushbeams) with Visual Product Development and Flow Simulation Behaviour software "Discrete Element Modeling" (DEM) shows smart-drive extended penetrations are possible, evenso under steep inclined angles from horizontal to more than 30 degree downhole. In case of significant steep mining the new mining method phrase should be "Directional Mining", dry or wet, Dewatering is developed or Cutting & Dredging through Screw-Transporters are proactive in developing roadmap of the leading global Highwall mining company.The large impact of surface mining on the topography, vegetation, and water resources has made it highly controversial.Surface mining is subject to state and federal reclamation requirements, but adequacy of the requirements is a constant source of contention. Unless reclaimed, surface mining can leave behind large areas of infertile waste rock, as 70% of material excavated is waste.In the United States, the Surface Mining Control and Reclamation Act of 1977 mandates reclamation of surface coal mines. Reclamation for non-coal mines is regulated by state and local laws, which may vary widely.Human healthThe United Mine Workers of America has spoken against the use of human sewage sludge to reclaim surface mining sites in Appalachia. The UMWA launched its campaign against the use of sludge on mine sites in 1999 after eight UMWA workers became ill from exposure to Class B sludge spread near their workplace.[10]Environmental impactAccording to a 2010 report in the journal Science, mountaintop mining has caused numerousWikimedia Commons has media related to Surface mining .environmental problems which mitigation practices have not successfully addressed. For example,valley fills frequently bury headwater streams causing permanent loss of ecosystems. In addition,the destruction of large tracts of deciduous forests has threatened several endangered speciesand led to a loss of biodiversity.[11]John Grisham's novel Gray Mountain (2014) addresses strip-mining and its deleteriousimpacts in the Appalachians.John Prine's song Paradise is about the destruction of parts of Kentucky by coal mining.Shaft miningMontrie, Chad (2003). To Save the Land and People: A History of Opposition to Surface Coal Mining inAppalachia . United States: The University of North Carolina Press. p. 17. ISBN 0-8078-2765-7.1. "Where Is Coal Found?". World Coal Association. Retrieved 28 June 2011.2. "Gallery". Kentucky Coal .3. Gardner, J.S. & Sainato, P . (March 2007). "Mountaintop mining and sustainable development inAppalachia". Mining Engineering . pp. 48–55.4. "Mountaintop Mining/Valley Fills in Appalachia: Final Programmatic Environmental Impact Statement".U.S. Environmental Protection Agency . October 25, 2005. Retrieved August 20, 2006.5. Jessica Tzerman (August 3, 2006). "Blast Rites". Grist . Retrieved September 4, 2006.6. "Appalachian Regional Reforestation Initiative Forest Reclamation Advisory"(PDF). Office of SurfaceMining and Reclamation . Retrieved July 11, 2007.7. "Biology: Plants, Animals, & Habitats - We live in a hot spot of biodiversity". Apalachicola RegionResources on the Web . Retrieved September 18, 2006.8. "Appalachian Regional Reforestation Initiative". . Retrieved September 5, 2006.9. "Defender"(PDF). United Mountain Defense . 2006.10. Palmer, M.A. et al. (148). "Mountaintop Mining Consequences". Science 327.11. "Why Surface Mine?" ( /pdf/fact_sheets/why_surface_mine.pdf), an argument in favor of surface mining, by an executive of International Coal Group"The Truth About Surface Mining" (), a websitecreated to address misconceptions of mountaintop mining (MTM), most specificallymountaintop coal mining.Retrieved from "https:///w/index.php?title=Surface_mining&oldid=701636480"Categories: Surface mining Environmental issues with miningThis page was last modified on 25 January 2016, at 18:12.Text is available under the Creative Commons Attribution-ShareAlike License; additionalterms may apply. By using this site, you agree to the Terms of Use and Privacy Policy.Wikipedia® is a registered trademark of the Wikimedia Foundation, Inc., a non-profit organization.。
flow3d单词翻译
Delete source bitmap files--删除原位图文件Frame rate--帧速率A VI capture--动画捕捉A VI filename--动画文件名FLOW-3D (R)--FLOW-3D 简体中文版About--关于Interface version--接口版本Solver version--求解器版本Number of Processors--处理器数量GL_VENDOR<translation>Total Physical Memory (RAM)--物理内存总数(RAM)f3dtknux_license_file--授权许可文件F3D_HOME<translation>GL_RENDERER<translation>Host Name--主机名GL_VERSION<translation> F3D_VERSION--软件版本Operating System--操作系统Type--类型Porous--孔隙Porosity--孔隙率Lost foam--消失模Standard--标准Thermal conductivity--导热率Material name--材料名称Custom--自定义Surface area multiplier--面积倍增Unit system--系统单位Solid properties--固体属性Initial conditions--初始化条件Surface properties--表面属性Solids database--固体数据库Surface roughness--表面粗糙度Temperature--温度Temperature variables--温度变化Basic--基础Other--其他Saturation temperature--饱和温度Units=CGS--单位=公制Solutal expansioncoefficient--溶质膨胀系数Ratio of solute diffusioncoefficient--比溶质扩散系数Surface tension--表面张力Gas constant--气体常量Thermal conductivity--导热率Surface tension coeff--表面张力系数Critical solid fraction--关键凝固比率Solidus temperature--固相线温度Phase change--相变Material name--材料名称Thermal properties--热性质Custom--自定义Constant thinning rate--不断变薄率Units=SI--单位=国际单位制Partition coefficient--分隔系数Dielectric constant--介电常数Specific heat--比热Eutectic temperature--低共熔温度Coherent solid fraction--凝固Thermal expansion--热膨胀Unit System--系统单位Units=custom--单位=自定义Units=slugs--单位=斯勒格Reference temperature--起始温度Latent heat of vaporization--汽化潜热Reference solute concentration--参考溶质浓度Pure solvent melting temperature--熔点温度Liquidus temperature--液相温度Viscosity--黏度Solidification--凝固Vapor specific heat--蒸气比热Density--密度Temperature sensitivity--温度敏感性Saturation pressure--饱和压力Temperature shift--温度变化Compressibility--可压缩性Contact angle--接触角度Latent heat of fusion (fluid 1)--熔解潜热(流体1)Fluid 1--流体1New fluid database--新流体数据库Accommodation coefficient--调节系数Strain dependent thinningrate--应变黏度系数Constant thickening rate--不断增厚率'%s' added tomaterials database.--'%s' 添加到材料库.'%s' cannot beadded.Record already exists inmaterials database.--'%s' 不能被添加.在材料库已经存在该记录.New '%1'saved in materials database.--新'%1' 保存到材料库中.Could not find material DB' %1 '.--没有发现材料数据' %1 '.Add--添加Close--关闭Add Mesh Points--添加网点Direction--方向New Point--新的点Mesh Block--网格块2-D advanced options--2-D 高级选项Option--选项Add--添加Type:--类型:Component--组Cancel--取消Browse--浏览Source--来源File name:--文件名:Advanced--高级OK--确定Cancel--取消Numerics--数值运算Advanced options--高级选项ifslp=1<translation>OK--确定sigma--表面张力系数Air entrainment--卷气Air Entrainment--卷气Physics--物理Activate air entrainmentmodel--激活卷气模型idfair=1<translation>Air density--空气密度Surface tension coefficient--表面张力系数Dialog--对话框Remove mesh constrains--清除网格限制X Direction--X 方向Y Direction--Y 方向Z Direction--Z 方向Size of all cells--全部单元尺寸Total Cells--单元总数Check for updates:Unable to run f3dupdater(%1)--升级检查:不能运行升级程序(%1)Auto updater: Unable to run f3dupdater: %1--升级:不能运行升级程序(%1)Auto updaterUnable to run f3dupdater (%1)--自动升级不能运行升级程序(%1)Auto updaterUnable to find f3dupdater (%1)--自动升级不能运行升级程序(%1)Baffle options--隔板选项Baffle index--主隔板Baffle color--隔板颜色Hide selected baffles--隐藏选中的隔板Use contour color--使用轮廓颜色Selection method--择伐作业OK--确定Boundary type--边界类型Specified pressure--规定压力Grid overlay--网格重叠Specified velocity--指定速度Cancel--取消Velocities--速度Electric potential--电位Boundary--边界Stagnation pressure--滞止压力Pressure--压力V olume flow rate--体积流Z flow direction vector--Z 流向Y flow direction vector--Y 流向X flow direction vector--X 流向Density--密度W velocity-- W 速度V velocity-- V 速度U velocity-- U 速度Electric charge--电荷Mesh Block : #--网格块: #[ X Max Boundary ]-- [ X 最大边界][ Y Max Boundary ]-- [ Y 最大边界][ Z Max Boundary ]-- [ Z 最大边界]Mesh Block : #%1[ X Min Boundary ]--网格块: #%1 [ X最小边界]Mesh Block : #%1[ %2 Boundary ]--网格块: #%1[ %2 边界][ Y Min Boundary ]-- [ Y 最小边界][ Z Min Boundary ]-- [ Z 最小边界]Type--类型Solid--固体X low--X 低点Y low--Y 低点Z low--Z 低点Add to component--添加为元件X high--X 高点Y high--Y 高点Z high--Z 高点Transform--转换OK--确定Specific heat--比热Physics--物理Auto--自动OK--确定Cancel--取消Physics--物理Simulate--仿真Stop preprocessor--停止预处理Cancel--取消Preview--预览Preview / Simulate--预览/仿真Block distribution--块分配Porous--孔隙OK--确定Component--组Cancel--取消Scalars--标量Type--类型Angle--角度Solid--固体Add to component--添加为元件Height--高度Transform--转换Max--最大Min--最小Cell size--单元尺寸Render space dimensions --渲染面积"Cell size" isempty.--"单元尺寸"为空.Max--最大Min--最小Create mesh block(Cylindrical)--创建网格块(柱状)Total number of cells--单元数量Type--类型Solid--固体Z low--Z 低点Cylinder subcomponent--子气缸Add to component--添加为元件Radius--半径Z high--Z 高点Transform--转换%n days--%n 天Setting the defaultworkspace location isrequired. You can changethe location at any timefrom the Preferences menu.--需要设置本地默认工作区位置.你可以随时通过菜单来改变位置。
SIMOCRANE CenSOR V3.0 HF1 商品说明书
SIMOCRANE CenSORV3.0 HF1These instructions take precedence over statements in other documents.Please read the instructions carefully since important information for installation and use of the software is included for you.In version V3.0 HF1 of the "SIMOCRANE CenSOR", the surface of the existing reflectors was replaced by a new, innovated surface. The new surface is a white/black printed reflective foil with a higher reflection class.In this version no changes are made in the camera HW and SW.The new reflectors are mounting compatible with the previous version. The camera system has remained functionally compatible with the new reflectors.Contents1 SCOPE OF DELIVERY1.1 DVD1.2 Runtime Licensing1.3 License conditions and disclaimer of Third-Party Software2 INSTALLATION INSTRUCTIONS2.1 Mounting and connecting2.2 Installation2.3 Uninstalling3 BOUNDARY CONDITIONS AND FUNCTIONAL RESTRICTIONS1 Scope of deliveryThe package “SIMOCRANE CenSOR V3.0 HF1” Outdoor Variant contains:Stainless steel housing including the camera “SIMATIC MV540 H CRANES”, IR flash and cable assembliesProduct DVDLicensing noticeMounting instructionsRetroreflective reflector (separate MLFB number)The package “SIMOCRANE CenSOR V3.0 HF1” Indoor Variant contains:Camera SIMATIC MV540 H CRANES, IR flash and cable assembliesProduct DVDLicensing noticeMounting instructionsRetroreflective reflector (separate MLFB number)The package “SIMOCRANE CenSOR V3.0 HF1” Reflectors contains:Retroreflector 300X300 mm 6GA7201-1AA01-0AA0Retroreflector 500X500mm 6GA7201-1AA02-0AA0The following software versions are associated:1.1 DVDThe software DVD (A5E50891177/002-2-DVD SIMOCRANE CenSOR V3.0 HF1) contains: Readme fileLicense agreementsSoftwareLinkDownloadPronetaMMI-Diagnose-ToolGSD file for SIMATIC MV540 H CRANESDocumentationManual in GermanManual in EnglishMounting Instructions camera/reflector in German/EnglishElectric circuit diagramDVD structure treeLimitation of liabilityFor the IMM Diagnostics ToolThe diagnostic tool and the corresponding documentation contained on the software DVD are provided free of charge. The customer is granted the non-exclusive, non-transferable, gratuitous right to use the software. This includes the right to change the software, to copy it unchanged or changed and to combine it with customer's own software.Governed by German law. Place of jurisdiction shall be Erlangen.Safety instructionsSiemens provides products and solutions with industrial security functions that support the secure operation of plants, solutions, machines, equipment and/or networks. They are important components of a holistic industrial security concept. The products and solutions from Siemens are continuously developed with this aspect in mind. Siemens recommends strongly that you regularly check for product updates.For the secure operation of Siemens products and solutions, it is necessary to take suitable preventive action (e.g. cell protection concept) and integrate each component into a holistic, state-of-the-art industrial security concept. Any third-party products that may be in use must also be taken into account. You will find more information about industrial security at:/industrialsecurityConstantly up-to-date information on SIMOCRANE products, product support, FAQs can be found on the Internet: https:///cs/ww/de/ps/200871.2 Runtime LicensingThe device is delivered with installed software. Please pay attention to the license agreements. Further information to the license agreements you will find the documents in ReadMe_OSS.zip on DVD.1.3 License conditions and disclaimer of Third-Party Software (e.g.Open Source Software and other License software)The product "SIMOCRANE CenSOR V3.0 HF1” contains unchanged Third Party Software or software changed by us. Please read the documents in ReadMe_OSS.zip on DVD carefully.2 Installing instructions2.1 Mounting and connectingThe instruction for mounting and connecting of SIMOCRANE CenSOR V3.0 HF1 is part of the manual "SIMOCRANE CenSOR Operating Instructions", edition 07/2021 as well in the mounting instructions on DVD.2.2 InstallationThe camera SIMOCRANE CenSOR MV540 H CRANES is equipped with a Web server that provides Web-Based Management (WBM). You can set up and configure your camera using the WBM. You can create crane-specific programs and perform diagnostics.The connection between camera und laptop / pc is via Ethernet. The WBM can be accessed via a Web browser such as Microsoft Internet Explorer or Google Chrome.This construction has the following advantages:You do not have to install the software on your laptop / pc.You can start the WBM from any laptop / pc.For the first commissioning, you need application software, e.g., the Proneta tool for setting the address of SIMATIC NET Industrial Ethernet products. PRONETA can be found in your SIMATIC installation or as a free download on the website of Siemens Industry Online Support.https:///cs/ww/en/view/109781284With this application software you can determine and change the current IP address and the device name.The detailed procedure can be found in the manual "SIMOCRANE CenSOR Operating Instructions", edition 07/2021, Chapter 7.2.3 UninstallingThe installed Proneta-Tool can be uninstalled via Windows Start Settings Control Panel Software.3 Boundary conditions and functional restrictionsThe PROFINET communication with SIMOTION D 435-2 DP/PN onboard is not released.The ProfiNet connection between the SIMOCRANE CenSOR V3.0 HF1 and the SIMOTION D435-2 may lead to communication errors.RemedyThe communication to SIMOTION D435-2 should be made per UPD interface or per additional module CBE30-2.MMI-Diagnostics tool sporadic interruption during recodingMMI Diagnostics tool may not start the recordings correctly. This can be seen that the numberof images in the MMI Diagnostic Tool does not increase.Remedy:Restart the MMI diagnostic toolA training course by instructed personnel before a commissioning is recommended. This training course can be ordered optionally.End。
冷原子光谱法 英语
冷原子光谱法英语Okay, here's a piece of writing on cold atom spectroscopy in an informal, conversational, and varied English style:Hey, you know what's fascinating? Cold atom spectroscopy! It's this crazy technique where you chill atoms down to near absolute zero and study their light emissions. It's like you're looking at the universe in a whole new way.Just imagine, you've got these tiny particles, frozen in place almost, and they're still putting out this beautiful light. It's kind of like looking at a fireworks display in a snow globe. The colors and patterns are incredible.The thing about cold atoms is that they're so slow-moving, it's easier to measure their properties. You can get really precise data on things like energy levels andtransitions. It's like having a super-high-resolution microscope for the quantum world.So, why do we bother with all this? Well, it turns out that cold atom spectroscopy has tons of applications. From building better sensors to understanding the fundamental laws of nature, it's a powerful tool. It's like having a key that unlocks secrets of the universe.And the coolest part? It's just so darn cool! I mean, chilling atoms to near absolute zero? That's crazy science fiction stuff, right?。
金属面绝热夹芯板围护系统抗风性能研究
中国建筑防水China Building Waterproofing2019年第5期5月2019 No.5MayD01:10.15901/ki,1007-497x.2019.05.011金属面绝热夹芯板围护系统抗风性能研究唐潮,王保强(多维联合集团有限公司,北京100070)摘要:针对金属面绝热夹芯板墙面围护系统风揭破坏的现状,结合抗风揭试验及工程实践,分析了其建筑构造、受力机 制及破坏原因,并对现行规范要求飽夹芯板墙面系统进行了测试与评价,提出了夹芯板系统抗风设计建议及螺钉加强设计建议,为今后夹芯板围护系统工程的设计提供参考。
关键词:金属面绝热夹芯板;隐钉连接;抗风揭;标准规范;自攻螺钉文章编号:1007-497X (2019)-05-0038-06中图分类号:TU501 ;TU57+8 文献标志码:AStudy on Wind Resistance Performance of Metal SurfaceInsulation Sandwich Panel Envelope SystemTang Chao,Wang Baoqiang(Duowei Union Group Co., Ltd., Beijing 100070, China)Abstract : In view of the status of wind damage of metal surface insulation sandwich panel wall envelope system, combinedwith uplift test and engineering practices, the construction structure, force mechanism and damage reasons are analyzed, andthe sandwich panel wall required by current regulations is tested and evaluated. The windproof design proposal of thesandwich panel system and the screw reinforcement design proposal are put forward, which provided reference for design of the sandwich panel enclosure system project in the future.Key words : metal surface insulation sandwich panel; hidden nail connection; wind resistance; standard specification : self tapping screw0前言随着国民经济的发展,建筑技术空前进步,金属围护系统因其质量轻、施工快捷、外形美观,易于实现 各种奇特新颖建筑造型,在工业与民用建筑领域中得到了广泛应用。
风能基础知识PPT(英文版)
Contents
Wind Power: Talk 1
• Why wind? • How wind turbines
work • The power in the
wind
Key factors in wind power
• Wind consistency (how much of the time does the wind blow, at a useful speed?)
• Wind speed (how high is the average wind speed?) • Spacing of turbines in the array (are they far enough apart to
require yaw device
• Vertical axis
– Don’t need to point into the wind
– Easy to construct
– Less efficient – Mounted lower, less
wind – More turbulent, stress
access undisturbed wind?) • Size of turbines (how large is the area of e circle covered by
the blades?) • How large an area of land (or sea) can be dedicated to the
Why wind?
• Wind is widely available • Largely independent from imports,
onsurfacetextureavailable
Surface Textures available have revolutionized the home design and decoration industry. With so many options available, it has become easier and more enjoyable to decorate and spruce up your home.Surface textures are all the different materials, patterns, and shapes that enhance the visual appeal of your home. They can range from the luxurious, classic look of marble to the modern, contemporary look of glass or concrete to the old-school lead- and tin-lined textured of wainscot. You can create custom textures to fit any desired look and feel or to match existing home decor.Surface textures can be used all around the house, both indoors and outdoors. Surface texture can be applied to walls, ceilings, and floors as well as furniture and cabinetry. The texture can range from the subtle, soft texture of suede to the classic, slatted look of wood to the vivid visual texture of a bold mural. The textured surface has more depth that can be used to accentuate a room, add visual interest and help hide imperfections in the walls.Surface textures can also be used to give furniture and cabinetry a unique look. Whether it is a mix of woods and metals or a vintage finish to a piece, it can easily be achieved with the right surface texture. Surface texture can also be used on decorative pieces such as lampshades, doors, and accessories to add texture and interest to a room.Surface textures come in many different finishes, from glossy to matte, glossy to metallic, glossy to rustic and from smooth to rough. This makes it easier to find surface textures that are aesthetically pleasing and that will fit into your existing design scheme.Surface textures available have opened up a world of possibilities for home design and decorating. By utilizing the range of textures, it has become easy to find the perfect look for your home, both indoors and outdoors. With somany options available, it has become easier and more enjoyable to decorate and spruce up your home.。
Surfaces and Interfaces in Liquid Crystal Devices
Surfaces and Interfaces in LiquidCrystal Devices液晶设备中的表面与界面液晶是一种特殊的物质,它既具有流动性又有晶体的特征。
因此,在液晶设备中,表面和界面的性质对其性能有着极其重要的影响。
本文将从表面和界面两个方面分析液晶设备的性能。
一、表面的影响表面是液晶分子与外界之间的直接接触点,同时也是液晶分子之间交换信息的重要媒介。
表面的化学性质、形貌和排列方式对液晶分子的取向、流动行为和长程序列有着重要的影响。
化学性质表面的化学性质主要指表面分子与液晶分子之间的亲疏性。
在液晶设备中,通常采用的是硅、金属或单晶硅等材料作为基板。
而这些材料表面本身是非常亲疏分明的,亲水性强的基板表面容易吸附水分和杂质,形成原子层,导致液晶分子的取向不稳定;反之,疏水基板则容易吸附空气、水分和其他杂质,对液晶分子的取向产生干扰。
形貌表面形貌对液晶分子取向和流动行为的影响不容忽视。
表面的粗糙度、纹理和凹凸不平都会影响液晶分子的分布和取向。
因此,为了保持液晶分子的有序排列,制造液晶设备的表面要求越平整越好。
排列方式表面的排列方式对液晶分子的取向、流动行为和长程序列也起着决定性作用。
不同的排列方式会对电流、温度、压力和震动等外部因素的响应方式产生影响。
液晶设备制造中广泛采用的有几种基本的排列方式,包括平行排列和垂直排列等。
二、界面的影响在液晶设备中,不同的物质之间的交界面称为界面。
液晶分子与基板、液晶分子之间或不同液晶之间的界面对设备性能都有着直接的影响。
基板与液晶之间的界面在液晶平板显示器中,液晶分子通常位于两片玻璃基板之间。
基板表面的处理方式和涂层的性质对液晶分子取向和流动行为具有决定性影响。
例如,在基板表面处理时使用非对称性的光敏材料,可以产生大约20°的预铺排列,有利于液晶分子的取向。
在液晶分子与基板之间形成的层状结构中,极性基团要尽可能地避免与液晶分子之间的共价键或金属键相互作用,以达到最佳的液晶状态。
wind波动率曲面代码
wind波动率曲面代码摘要:1.引言2.风波动率曲面的基本概念3.风波动率曲面的计算方法4.风波动率曲面的应用领域5.风波动率曲面的代码实现6.总结与展望正文:【引言】风能作为一种清洁的可再生能源,在我国得到了广泛的应用。
风波动率曲面是研究风能资源的重要工具,对于风电场的规划、设计和管理具有重要意义。
本文将对风波动率曲面的相关知识进行介绍,并给出代码实现方法。
【风波动率曲面的基本概念】风波动率曲面(Wind Power Density Surface)描述了某一高度范围内风能资源的空间分布情况,通常以单位时间内的平均风功率密度表示。
风波动率曲面可以根据历史观测数据、数值模拟等方法获得。
【风波动率曲面的计算方法】风波动率曲面的计算方法主要包括插值法、数值模拟法等。
其中,插值法是最常用的方法,可以通过已有的观测数据来预测未知区域的风能资源。
常用的插值方法有反距离加权法(IDW)、自然邻域法(Kriging)等。
【风波动率曲面的应用领域】风波动率曲面在风电场规划、设计和管理等领域具有广泛的应用。
在风电场规划阶段,风波动率曲面可以用于评估风能资源的潜力,为风电场选址提供依据;在风电场设计阶段,可以根据风波动率曲面分析风电场的发电量,为风电场优化设计提供参考;在风电场管理阶段,风波动率曲面可以用于评估风电场的运行状况,为风电场运行决策提供支持。
【风波动率曲面的代码实现】本文将以Python 语言为例,介绍风波动率曲面的代码实现。
首先,需要安装相关库,如numpy、matplotlib 等。
然后,可以使用scipy 库中的interpolate 模块实现风波动率曲面的插值计算。
以下是一个简单的示例代码:```pythonimport numpy as npimport matplotlib.pyplot as pltfrom scipy.interpolate import griddata# 历史观测数据x = np.array([100, 200, 300, 400, 500])y = np.array([100, 200, 300, 400, 500])z = np.array([200, 250, 300, 350, 400])# 插值方法xi, yi = np.mgrid[0:500:20, 0:500:20]zi = griddata((x, y), z, (xi, yi), method="cubic")# 绘制风波动率曲面图plt.contourf(xi, yi, zi, 20, cmap="jet")plt.scatter(x, y, c="k", marker="o", s=80)plt.colorbar()plt.title("风波动率曲面图")plt.xlabel("x 轴")plt.ylabel("y 轴")plt.show()```【总结与展望】风波动率曲面是研究风能资源的重要工具,对于风电场的规划、设计和管理具有重要意义。
物理试题练习题教案学案课件土壤物理题库.doc
土壤物理题康1.Prove the following relation of porosity to particle density and to bulk density: /=(ps- pb)/p s =1 - pb/p s2.Prove the following relation between volume wetness, mass wetness, bulk density, andwater density (p w = M W A^W):0 = W pb/pw3. A sample of moist soil having a wet mass of 1.0 kg and a volume of 0.64 liter (6.4x10-4 m3)was dried in the oven and found to have a dry mass of 0.8 kg. Assuming the typical value of particle density for a mineral soil (2650 kg/m3), calculate the bulk density pb, porosity /, void ratio e, mass wetness w, volume wetness 0, water volume ratio v w? degree of saturation s, and air-filled porosity /a-4.What is the equivalent depth of water contained in a soil profile 1 m deep if the masswetness of the upper 0.4 m is 15% and that of the lower 0.6 m is 25%? Assume a bulkdensity of 1200 kg/m3 in the upper layer and 1400 in the lower layer. How much water does the soil contain in cubic meters per hectare of land?5.Give two bubble in a glass of carbonated water, one with a radius of 0.5 mm and the otherwith a radius of 1.5 mm, what is the pressure difference between them? Assume y = 0.07 N/m.6.Calculate the equilibrium capillary rise of water and mercury at 20°C in glass cylindricalcapillary tubes of the following diameters: (a) 2 mm; (b) 0.5 mm; (c) 0.1 mm. Disregard density of atmosphere.7. A capillary tube with an internal radius r = 0.25 mm is dipped into water of surface tension0.073 N/m. How high will the water rise in the tube if the contact angle a = 0°, and how highif a = 45°?8.The bottom of a capillary tube is immersed in a water reservoir. Water then rises in the tubeand comes to rest at a height of 50 mm above the free water surface. The tube is then lifted slowly until the water in it begins to recede down the tube. After the lifting is stopped, the meniscus inside the tube comes to rest at a height of 57.5 mm. Assuming that the receding contact angle of water in the tube is 0°, calculate: (a) the radius of the tube; (b) theadvancing contact angle. Use a value of 0.0705 N/m for the surface tension of water.ing Stokes9s law, calculate the time needed for all sand particles (diameter > 50 pm) tosettle out of a depth of 0.2 m in an aqueous suspension at 30°C. How long for all siltparticles to settle out? How long for "coarse" clay (>l(im)?10.Calculate the approximate specific surface of a sand composed of the following array ofparticle size:Average diameter: 1mm 0.5mm 0.2mm 0.1mmPercent by mass: 40% 30% 20% 10%11.Calculate the bulk density of a soil sample that has a wet weight of 15.2g, a dry weight of14.5g, and a volume of 12.1cm3.12.A soil sample has a bulk density of 1.12 Mg/m3 and a particle density of 2.62 Mg/m3.Calculate the total porosity of the soil.13.Calculate the aeration porosity of a soil sample that has a bulk density of 1.35 Mg/m3, aparticle density of 2.65 Mg/m3, and a gravimetric soil water content of 0.18 kg/kg14.How many centimeters of a rainfall would be required to bring a soil from a water contentof 0.08kg/kg to 0.25 cm3/cm3 at a depth of 15 cm if the bulk density of the soil was 1.35 Mg/m315.Calculate the potential gradient between two points 20cm apart in vertical distance andreading 20 b and 20 cm of Hg, respectively.16.A tensiometer is buried in an unsaturated soil sample at a depth of 15cm below the soilsurface. The surface of the mercury reservoir is 10cm above the soil surface, and themercury-water interface in the tube connecting the tensiometer to the mercury is 20cm above the soil surface. What is the matric potential of the soil sample in headunits(centimeters of water)?17. A 10-cm-volume of soil sample weighs 15g before drying and 13g after drying. Calculate(a)bulk density, (b) volumetric water content, (c) gravimetric water content, (d) totalporosity, (e) air-filled porosity of the sample. (Assume a particle density of 2.6g/cm3.) 18.A soil clod has a volume of 100cm3, gravimetric moisture content is 0.20, and bulk densityis 1.50 g/cm3. Calculate the degree of saturation and air-filled porosity ?19.Water is ponded on the surface of a saturated soil core to a constant depth of 10cm.Assuming that the core has a cross-sectional area of 28.3cm2 and a height of 10cm, and that 425cm3 of water is collected in the beaker in 4 hours , calculate the saturated hydraulic conductivity and flux density of the soil. Place the reference level at the top of the core.20.A vacuum gage tensiometer, (full scale 0-100), reads 34. The distance from the gage to theceramic cup (vertical distance) is 100cm. Find the matric potential, \|/m21.The distance from the surface of the mercury reservoir to the center of the ceramic cup(vertical distance) is 20cm and the value of mercury height is 14.2cm. Find the matric potential, \|/m ?22.Calculate the equivalent diameter of the pores filled with water that can be maintained at amatric head of 100cm at equilibrium and a soil temperature of 20 °C ? Surface tension ofwater is 72dynes/cm at 20 °C23.How many centimeters (equivalent depth) of water are contained in a soil profile Im deep ifthe mass wetness of the upper 40cm is 15 %, and that of the lower 60cm is 25 % ? The bulk density is 1.2 g/cm3 in the upper layer and 1.4g/cm3 in the deeper layer. How much water does the soil contain in cubic meters per hectare of land ?24.Consider a soil core of equal diameter and length of 0.08m. Water is allowed to flowvertically downward under a constant head of 0.04m. The constant rate of effluent collected from bottom of core was 0.04m/s. Calculate the saturated hydraulic conductivity of soil.25.A soil in which the liquid water is in equilibrium with a water table at -70cm and thereference level is chosen as -70cm. Find the values of \|/P (pressure potential), \\f m (matric potential), \|/g (gravitational potential), \|/h (hydraulic potential) throughout the soil profile to -110cm ?26.A soil in which water is flowing into a drain at -40cm. The reference level is the soil surface.Find the values of\|/p (pressure potential), \\f m (matric potential), \|/g (gravitational potential), \|/h (hydraulic potential) for the entire soil profile to -60cm. Estimates must first be made of % ?27.Suppose you measured the following data for a soil. A horizon from 0 to 30cm with bulkdensity=1.2 Mg/m3: 0m(gravimetric water content)=28 % at -lOkpa, 20 % at -lOOkpa, and 8 % at -1500kpa. Bt horizon 30 to 70cm with bulk density=1.4 Mg/m3: 0m(gravimetric watercontent)=30 % at -lOkpa, 25 % at -lOOkpa, and 15 % at -1500kpa. Bx horizon from 70 to 120cm with bulk density=1.95 Mg/m3: 0m(gravimetric water content)=20 % at -lOkpa, 15 % at -lOOkpa, and 5 % at -1500kpa. Estimate the total available water holding capacity of the soil ?28.A one hectare field contains 0.2 g g-1 of water to 10 m depth. Assuming a uniform soil bulkdensity of 1.5 Mg/m3, calculate the total water content of soil in liters and equivalent depth.29.The 0-50 cm layer of a lakebed soil has a field capacity of 30% by weight, soil-watercontent of 15% by weight, and bulk density of 1.2Mg m-3. A rainfall of 4 cm was received of which 75% was lost as runoff. Calculate the following:1.What is the volume of runoff from a test plot of 25m * 40m?2.What is soil erosion (t/ha) if the runoff contained sediments of 25 g / liter?30.A soil is sampled by a core measuring 7.6 cm in diameter and 7.6 am deep. The core weighs300 g. The total core plus wet soil weight is 1000 g. On oven drying at 105°C the core plus dry soil weighed 860 g. Calculate wet and dry bulk densities and gravimetric moisturecontents.31.One liter of dry soil sampled from a farm requires 300 g of water to completely saturate it.Calculate: (a) its porosity and (b) volume of water required to saturate the plow layer (20 cm) of 1 hectare of the farmland.32.A soil in the greenhouse container has a wet bulk density of 1.7 Mg/m3 and dry bulk densityof 1.4 Mg/m3. Calculate gravimetric and volumetric soil moisture contents, and air-filled porosity.33.Calculate particle density of a soil from the following data:Weight of pycnometer= 50 gWeight of the powder dry soil= 214 gMass of soil and deaerated water when pycnometer was filled to capacity + pycnometer = 352gTemperature of water = 20°CVolume of pycnometer = 168 cm334.A sample of moist soil weighed 100 g and had an oven dry moisture content of 0.04. What isthe oven dry weight of the 100 g sample?35.10 mm of rain infiltrated a soil having aninitial moisture content by volume of 0.1 m3/m3. If the soil absorbed enough of the rainfall to raise its moisture content to 0.2 m3/m3, how many cm would the rainfall penetrate?pute soil moisture content of a 20 g of wet sample that registers an increase in volumeby 5 cm3. Assume particle density is 2.7 g/cm3.37.The following soil data were obtained fbr an irrigation experiment with com. Irrigation of 10cm was applied on 6/10/88 after monitoring the soil moisture.Soil moisture contentBulk Wilting Field (g/g)Depth density point capacity —(cm) (g/cm3) (w, g/g) (w, g/g) 6/10/88 6/20/880-30 1.2 0.10 0.30 0.10 0.2031-50 1.3 0.12 0.32 0.15 0.2551-80 1.4 0.14 0.28 0.25 0.2081-150 1.6 0.15 0.25 0.20 0.15(a)Calculate depth of penetration of irrigation water(b)Evaluate evaportranspiration of com in mm/day(c)Determine drainable porosity at field capacity assuming particle 2.65 g/cm weight of a wet soil core 7.5 cm in diameter and 7.5 cm deep is600 g. Calculate wet and dry density and equivalent depth of water if the oven dry weight of the core is 500 g.39.Point A is 10 cm above point B in a soil. At point A, \|/g (gravitational potential) =15 cm.What is \|/g (gravitational potential) at point B ?40.If a tensiometer functions in the range of \|/m (matric potential) from 0 to -800cm, what is thelargest effective pore radius of the ceramic material making up the tensiometer cup ?。
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a r X i v :c o n d -m a t /9910175v 1 [c o n d -m a t .m t r l -s c i ] 12 O c t 1999Surface Instability in Windblown Sand Douglas A.Kurtze Department of Physics,North Dakota State University,Fargo,ND 58105-5566,USA Joseph A.Both and Daniel C.Hong Department of Physics,Lewis Laboratory,Lehigh University,Bethlehem,PA 18015,USA Abstract We investigate the formation of ripples on the surface of wind-blown sand based on the one-dimensional model of Nishimori and Ouchi [Phys.Rev.Lett.71,197(1993)],which contains the pro-cesses of saltation and grain relaxation.We carry out a nonlinear analysis to determine the propagation speed of the restabilized rip-ple patterns,and the amplitudes and phases of their first,second,and third harmonics.The agreement between the theory and our nu-merical simulations is excellent near the onset of the instability.We also determine the Eckhaus boundary,outside which the steady ripple patterns are unstable.PACS numbers:47.54.+r,45.70-n,92.10.Wa 1Introduction Since the pioneering work of Bagnold [1],many researchers have investigated the complex dynamics of dry granular materials at a surface [2-6].Dry gran-ular materials are assemblies of macroscopic objects that interact with each other essentially via a hard core repulsive potential.Hence they are loosely connected,particularly at the surface.When those grains at the surface are exposed to a wind,they can readily be ejected and carried by the wind until gravity eventually pulls them back to the surface.The dynamics of a single grain is rather simple,given by the Newtonian trajectory of a point particle.Even so,experiments have shown that the collective response of the grains can become exceedingly complex,ranging from formation of simple ripple patterns to ridges and dunes to violent tornadoes [2].Our current under-standing of such complex phenomena remains mostly confined to compiling1data on experimental observations.With regard to the formation of ripple patterns,however,there have been some attempts to construct a simple yet physical continuum model.We will investigate the continuum model due to Nishimori and Ouchi [3].The Nishimori-Ouchi(NO)model of ripple patterns accounts for two elementary processes of sand transportation by the wind which have been identified by investigators in aeolian sand dynamics,namely saltation and creep[1,2].Saltation refers to the process by which surface grains are ejected into the air under the influence of a strong wind,and are blown downwind where they collide with other surface grains.There they transfer momentum to these downwind grains,which may themselves be ejected in turn,thereby continuing the process(see Fig.1).Creep is the surface movement of grains too heavy to be ejected into the air but light enough to be pushed along the surface.Creep also describes the surface movement of grains on hills under the influence of gravity.Previous studies based on the NO model have been confined largely to linear stability analysis and Monte Carlo simulations of a lattice version with simple rules for the grain dynamics[3,11].The purpose of this paper is to go one step farther by carrying out a nonlinear analysis of the continuum model and uncovering some of the features of ripple formation that are inaccessible to linear analysis.In particular,we carry out a weakly nonlinear analysis valid near the onset of instability of aflat sandbed to determine the amplitude,shape,and propagation speed of the ripple pattern that forms in this regime.We also compare these results with our numerical integrations of the model equa-tions.These computations are rather unusual because the model lacks an up-down symmetry,and especially because accounting for saltation makes the model nonlocal in space.Wefind,however,that the process of pattern selection in this simple one-dimensional system,in particular the selection of the wavelength and speed of the patterns[7],is similar to what is seen in more complicated multidimensional systems such as directional solidification[8]or directional viscousfingering[9].That is,the wavelength of thefinal pattern depends on the initial conditions,and may lie anywhere within a band of linearly stablefinal states.The stable band turns out to be somewhat wider than in most other models.In the next section we review the Nishimori-Ouchi model equations[3], point out a physical symmetry which they violate,and propose a simple modification of the model which respects that symmetry.In Section III we2carry out a linear stability analysis of theflat-sandbed solution of the model, both for the original Nishimori-Ouchi equations and for our modification.We extend this in Section IV to give a weakly nonlinear analysis for both forms of the model.Section V presents our numerical calculations and compares them with the results of the weakly nonlinear analysis.The results are discussedin thefinal section.2One-Dimensional Model for Windblown Sand The starting point of the Nishimori-Ouchi(NO)model[3]is a local conser-vation law for sand grains.Let h(x,t)be the local height of the sand bedat position x and time t,measured from some reference level.The height increases when grains are added at position x.We write∂h=Q nl,(1)∂xwhere J l(x,t)is a localflux of grains in the positive direction at x,andQ nl(x,t)is the net input of grains at x due to nonlocal processes.The expression for J l embodies a model of creep.Nishimori and Ouchi choose J l=−D(∂h/∂x).Note that this merely expresses the tendency of grains to roll downhill;it does not include any bias favoring motion in the direction of the wind.Saltation is modeled by gain and loss terms in the nonlocal transfer rateQ nl.Let N(x,t)denote the outward saltationflux of particles from x at time t.That is,let N(x,t)dx be the number of particles per unit time taking offfrom positions between x and x+dx.The loss term in Q nl is then−A N(x,t), where A is a scale parameter.The gain term is proportional to the rate at which particles arrive at x from other locationsξupwind of x.Suppose all particles which take offfrom the interval(ξ,ξ+dξ)subsequently land in the interval(x,x+dx).Then the number of particles per unit time landing in this latter interval of length dx is N(ξ,t)dξ,so the gain term in the saltationflux is then A N(ξ,t)(dξ/dx).It is possible to have more than oneξwhich satisfies this equation for a given x.That is,grains landing at x may have come from more than one takeoffpointξ.If this is the case,then the input term in the evolution equation should be summed over the different valuesofξ.3Note that evaluating N(ξ)at time t neglects theflight time of the incom-ing grains;we expect the evolution of the sandbed profile to take place on a much longer time scale than this,so that the time delay between takeoffand landing should be unimportant.Indeed,experiments on ripple formation by sand transported by water[10]show the evolution of the ripple pattern occurring on time scales of several hours.Combining the various contributions to theflux and substituting into the general conservation law for h gives the model evolution equation for the sandbed profile,∂h∂x D∂hdx−N(x,t) .(2)Note that this equation is nonlocal in x,as a result of the saltation gain term,which depends on conditions at a positionξwhich is afinite distance upwind of x.To complete the model,we must now specify the saltation function,an equation for theflight length of a single grain.In general,the locations x andξin the evolution equation will be related by x=ξ+L,where L is the horizontal length an ejected grain travels from takeoffto landing.This will depend on the size of the grain,its speed when it takes off,the wind velocity profile,and the topography of the sandbed itself.Nishimori and Ouchi proposed the simple ansatzL=L0+b h(ξ,t).(3) Here,L0is a parameter proportional to the shear stress of the wind at the surface,or more precisely to the friction velocity of the wind on the sand surface[11],and b in general depends on the average drag force on the grain. Nishimori and Ouchi took both L0and b to be constant,essentially assuming the wind velocity to be a constant,independent of x and t and unaffected by changes in the sandbed profile.Equation(3)merely indicates that the higher the takeoffpoint of a grain in saltation,the longer its trajectory.As Nishimori and Ouchi point out [3],this amounts to assuming that the height and topography at the point of landing may be neglected,and that only the surface height(as opposed to local topography)is important at the takeoffpoint.While this may be reasonable if h(x)is everywhere close to zero,it does violate a symmetry4of the physical problem,namely that the dynamics should be unaffected if we add any constant to h,thus changing our reference level.To restore this symmetry,it may be more appropriate to take the saltation function to beL=L0+b[h(ξ)−h(x)],(4) whereξis the takeoffpoint and x is the landing point.We will discuss the effects of this modification below.For convenience,we now put the model into dimensionless form.Taking L0,b and D to be constants,we choose L0to be the unit of horizontal length,L0/b to be the unit of vertical length(i.e.,of h),and L20/D to be the time unit.Further,we define J(x,t)=(AbL0/D)N(x,t),a dimensionless measure of the outward grainflux due to saltation.With these definitions, the evolution equation(2)becomes∂h∂x2+J(ξ,t)dξ∂t =∂2hdx−1 .(7)This is the form of the problem which we will analyze below,using both the NO saltation relation(6)and our symmetric modification of it,x=ξ+1+h(ξ,t)−h(x,t).(8) 3Linear Stability AnalysisWefirst note that aflat sandbed,h=h0=constant,is always a steady-state solution of the model,for either choice of saltation relation.For the symmetric saltation relation(8)this always givesξ=x−1,while for the5NO relation(6)we haveξ=x−1−h0.In the latter case,however,we may then redefine the length and time units–and the value of J–to map the solution with anyfinite h0(provided h0>−1)onto the solution with h0=0. Specifically,we would take the horizontal length unit to be L0(1+h0)instead of L0,and J would then be AbL0(1+h0)N/D rather than AbL0N/D.Thus we will take h=0to be the steady state whose stability we will investigate.When h is small,we may linearize the NO saltation relation to getξ≈x−1−h(x−1),(9) so that there is a single,uniqueξfor each x.From this we obtain dξ/dx= 1−h′(x−1),where the prime indicates partial differentiation with respect to x.The linearized evolution equation is then∂hnegative growth rates which are therefore suppressed in the solution.Thus we expect that solutions of the full differential equation will consist only of modes whose wave numbers are on the unstable side of the boundary.The onset of instability of theflat sandbed occurs at the value J c of J for which only a single mode,with wave number k c,is marginally stable and no other modes are unstable.These critical values may be determined by solving σ=0and dσ/dk=0simultaneously,which yieldsJ c sin k c=−k c,J c cos k c=−1.(15) Eliminating J c givestan k c=k c.(16) Thus the critical values are computed as k c=4.493and J c=4.603.The wavelength of the marginal mode(in units of L0)isλc=2π/k c=1.398, somewhat longer than theflight distance of a grain in saltation.For k=k c, the NO saltation relation leads toωc=−k c,so the phase velocity of the marginal mode is v=ωc/k c=−1.With the symmetric saltation relation we get v=−(1+J c)=−5.60.This is a surprising result of the model,that while the sand grains that form the ripples are blown downwind,the ripple pattern itself drifts upwind.The group velocity,however,is large and positive:From (14)we get dωk/dk=J(−k sin k+cos k),which goes to k2c−1=19.19at the critical point.For the symmetric saltation relation,the group velocity is lower by J,so at critical it is14.58.Note that all velocities are in units of D/L0.If we make the problem two-dimensional,allowing the sandbed to extend in both x and y directions,very little changes.The creep term in the evolu-tion equation becomes D∇2h,and as a result the expression forσk changes toσ(k,k y)=−k2−k2y−J k sin k,(17) where k is now the x component of the wave vector of the Fourier mode and k y is its y component.Clearly,the linear growth rate for a mode with nonzero k y is always less than the rate for the corresponding mode with k y=0.Thus we do not expect to see instabilities in which the transverse shape of the ripples becomes wavy,since thefirst instability to occur is against a mode in which the ripples are parallel to the y axis.74Nonlinear AnalysisWe now carry out a weakly nonlinear analysis to determine the amplitude, shape,and propagation velocity of the restabilized ripple patterns which form when J is slightly above its critical value J c.The nonlocality of the model, the dispersion in the imaginary part of the linear growth rate,and the lack of an up-down symmetry lead to some unusual features in the analysis.We begin with the assumption that the fundamental wave number k of the pattern which develops does not deviate much from the critical value k c when J is near J c.Hence we define a small parameterǫby settingJ=J c+ǫ2,(18) and then define a scaled wave number deviation q by writingk=k c+ǫq.(19) This is the appropriate scaling for the wave number because the stability boundary is approximately quadratic in k−k c and linear in J near its max-imum.Substituting these expressions into the linear growth rate(13)and expanding to second order inǫgivesσk=1J c−q2 +O(ǫ3).(20)Furthermore,from the expression(14)forωwefind that the phase velocity of the ripples is given byv=ω/k=−1+ǫk c q−1J c−q2 +O(ǫ3).(21)Thefirst stage of the nonlinear analysis consists of expanding the evo-lution equation(7)in powers of h,assuming the overall amplitude of h is small.To do this,we may rewrite the NO saltation relation(6)in the formξ=x−1−h(ξ,t),(22) repeatedly substitute this expression forξback into the h(ξ,t)on the right side,andfinally expand in powers of h.Differentiating the result with respect to x then givesdξ2[h2(x−1,t)]′′−1To third order in h,then,the evolution equation becomes∂h(x,t)2[h2(x−1,t)]′′−Jdxdx,(25)whereξ(x)is given by the saltation relation(6)and f is a test function which is integrable and infinitely differentiable,but otherwise arbitrary.We now change variables in this integral from x toξ,I f= ∞−∞f(ξ+h(ξ))dξ,(26) and expand the integrand in powers of h to getI f= ∞ k=01dξk h k(ξ)dξ.(27) Next we integrate the k th term by parts k times to getI f= f(ξ)∞ k=0(−1)k dξk dξ,(28) andfinally change variables again fromξto x≡ξ+1,I f= ∞−∞f(x−1)∞ k=0(−1)k dx k dx.(29)This result has the same form as the original expression for I f,but with dξ/dx replaced by an expansion.However,since the test function f is arbitrary, this requires the expansion and dξ/dx to be equal:dξk!d k h k(x−1)We now turn to the second stage of the calculation,namelyfinding so-lutions to the third-order approximation(24)to the evolution equation.We assume the solution will have a fundamental wave number k in the unstable range,with an amplitude of orderǫ.The quadratic terms in the evolution equation will then generate a Fourier component in the solution with wave number2k and possibly a constant term,and the cubic terms will lead to a component with wave number3k.Thus we writeh(x,t)≈ǫM(t)cos(kx−φ(t))+ǫ2M0(t)+ǫ2M2(t)cos[2(kx−φ(t))+θ2(t)]+ǫ3M3(t)cos[3(kx−φ(t))+θ3(t)]+···,(31) allowing phase differences among the various Fourier components.We sub-stitute this ansatz into the evolution equation and expand in powers ofǫ. Then the coefficients of cos(kx−φ(t))and sin(kx−φ(t))give equations for the fundamental amplitude M(t)and phaseφ(t):˙M=σk M−ǫ2Jk2M0M cos k−ǫ28Jk3M3sin k+O(ǫ4)(32)˙φ=ωk −ǫ2Jk2M0sin k−ǫ28Jk3M2cos k+O(ǫ4).(33)Evidently we need tofind M0,M2,andθ2in order to determine the am-plitude M and propagation velocity˙φ/k of the pattern.The x-independent term in the expansion of the evolution equation gives˙M0=0,so M0is in fact a constant;as argued above,we can choose it to be zero,so the M0 terms in the M andφequations can be dropped.The equations for M2and θ2come from the coefficients of cos(2kx−2φ+θ2)and sin(2kx−2φ+θ2)in the evolution equation.These are best written in the formddt M3e−iθ3=(σ3k+iω3k−3iωk)M3e−iθ3−98iJk3M3e3ik+O(ǫ2).(35)10Note that in the equation for˙M(t),all the terms on the right are of orderǫ2.Therefore M(t)changes on a long time scale of orderǫ−2,while M2andθ2vary on times of order unity.Thus we may regard M as a constant inthe equations for M2and M3.Sinceσ2k is negative,M2exp(−iθ2)goes to aquasi-steady state value which is proportional to M2.Substituting this valueinto the M equation gives˙M=σM−ǫ2λM3+O(ǫ4)(36)kThe analytical expression for the Landau constantλis complicated and un-enlightening;substituting(18)and(19)into it givesλ=16.905+64.680ǫq+O(ǫ2)(37)Note that the correction terms in the evolution equation for M,which wouldcome from including higher-order terms in the original expansions(24)forthe evolution equation and(31)for h(x,t),are of orderǫ4,notǫ3.As aresult,theǫ3terms in the equation come only from expanding the analytical expressions forσandλin powers ofǫ.This also holds for the equations forthe higher harmonics.Thus we get thefirst-order corrections to all of ourresults essentially for free.From(37)and the third-order expansion(20)forσk we obtain the steady-state amplitude M tofirst order inǫ,M2=(0.25946−0.59719q2)−(0.87725−2.10774q2)ǫq+O(ǫ2)(38)We thenfind the phase velocity,v ph=ω/k=−1+4.4934ǫq+(1.877−4.320q2)ǫ2−(3.439−10.128q2)ǫ3q+O(ǫ4),(39)and the group velocity,v gr=dω/dk=19.1907+13.4802ǫq+(18.241−40.984q2)ǫ2−(43.198−107.23q2)ǫ3q+O(ǫ4),(40)from(33).The equation(34)for M2andθ2givesM2/M2=0.908115+0.50118ǫq,θ2/π=0.22916−0.36189ǫq,(41)11and from(35)wefindM3/M3=1.52273+1.89385ǫq,θ3/π=0.4309−0.6024ǫq(42) As usual,the ripple solutions we have found are not all stable;instead, those with too large a wave number deviation q are linearly unstable.The calculation of the critical value of q is rather intricate,so we defer it to the Appendix.The result is that the range of stable wave numbers is rather wider than usual–it extends out to q=0.9095q0,where q0=(2/J c)1/2is the wave number deviation at whichσk vanishes to leading order inǫ.At the edge of the stable range,the amplitude M of the ripple solution is0.4157 times its value ay q=0.If instead of the NO saltation relation we use the symmetric relation(8), the results of the analysis are rather different.The expansion of dξ/dx is not as simple and clean as the derivation above;the evolution equation(24)is replaced by∂h(x,t)2{[h(x−1,t)−h(x,t)]2h′′(x−1,t)}′−J{[h(x−1,t)−h(x,t)][h′(x−1,t)]2}′+···(43)We again substitute the ansatz(31)into this equation and work out the Fourier components of the result.The equations for M andφbecome˙M=σkM−ǫ2Jk2M2M[cos k cosθ2−cos(2k−θ2)]+ǫ22Jk3M2(cos k−cos2k)(45) where nowωk is given by−J k(1−cos k)as is appropriate for this model. Note that the M0terms which were present in(32)and(33)are absent here;this is because the new saltation relation respects the symmetry under addition of a constant to h.The evolution of M2andθ2is now given bydand the third harmonic bydJk2e ik(1−e ik)(1+3e ik)MM2e−iθ223+5Numerical solutionsWe now present numerical solutions and compare them with the predic-tions made in the previous section.The nonlocal evolution equation(7) was solved numerically with periodic boundary conditions on a system of length l=2π/k,so that only the Fourier modes nk contributed to the solutions.For the discretization scheme,we chose an explicit method us-ing forward differences in time and central differences in space.The axis was discretized at29equally spaced sites with∆x=2π/k•2−9and solu-tions were generated forfive different values of J near J c=4.603,namely J=4.62,4.65,4.70,4.75,4.80,and values of k were chosen to span the un-stable region.Initial conditions were sinusoids of wave number k centered around h=0.At t=0,we start with a sinusoid at a particular wave number k,and let it evolve with(∆x)2/∆t=1/4until it reaches a steady state. This takes about106time steps.The nonlocal term in the evolution equa-tion,J(dξ/dx−1),was evaluated for a given x byfinding the nearest upwind value ofξsatisfying the equation x=ξ+1+h(ξ).Spefifically,thefirst root of the function f(ξ;x)=ξ+1+h(ξ)−x with value less than x was obtained by simplyfinding the two sites upwind of x and nearest to it between which f(ξ;x)changed sign.Then,dξ/dx was calculated using the values of h at these sites.Thefinal steady state,h(x,t),is then Fourier transformed,i.e.:h(x,t)=∞n=1[a n(t)sin nkx+b n(t)cos nkx],(54)from which we obtain M n=(a2n+b2n)1/2andθn=tan−1(b n/a n).Note that M1=M andθ1=φin this notation.The nonlinear analysis in the previous section predicts that these quantities will go to time-independent values.We find numerically that they actually oscillate as a function of time around their mean values.However,the magnitudes of these oscillations are quite small and decrease with increasing grid resolution,so we believe them to be numerical artifacts.We therefore take the time averaged mean values and compare them with the predictions of the weakly nonlinear analysis.We alsofind that although we start with an initial profile with the average height h0=0,the mean position of the steady state pattern shifts slightly upward in some cases,downward in others,to a small butfinite h0.Since the mean height of the sandbed is conserved by the exact evolution equation,14we believe that this is also a numerical artifact.Moreover,as mentioned in section2,we can map any steady state solution withfinite h0to the solution with h0=0by redefining the horizontal length scale from L0to L0(1+h0)and shifting the control parameter from J to J(1+h0).However, the magnitude offset h0was always of the order of10−5to10−3,and thus in all cases studied here,the corrections due to such an offset are quite negligible. Hence,our results without these corrections are virtually identical to those with corrections.Figure2shows the amplitude M of the fundamental mode as a function of k for different values of J.The data points are fairly close to the values predicted by thefirst-order expansion(38),which are represented by contin-uous curves.Note that the curves are asymmetric around the critical value k c and the asymmetry becomes more pronounced for larger J.The weakly nonlinear analysis is capable of predicting this asymmetry only because the order-ǫterms are included.In Figure3we plot the phase velocity of the fundamental mode against k for different values of J.The speed was obtained by calculatingφ(t)in the expression cos(kx−φ(t)),which is proportional to the fundamental mode in the steady state.The functionφ(t)was found to be linear in t,so v was calculated as v=dφ(t)/dt/k.The data points are compared against the weakly nonlinear predictions(solid line)given by(39).Only for fairly large J,and only near the high-wave-number end of the band of ripple solutions, does the velocity become positive,that is,in the direction of the wind.In Figures4a and4b are plotted the ratios of the amplitudes of the second and third harmonics to the appropriate powers of the fundamental ampltude,i.e.,R2=M2/M2and R3=M3/M3.The datafit quite well with the theoretical predictions for both cases,in particular near the onset k c=4.493,where the nonlinear analysis is most reliable.Note that the first-order terms in the analytical results match the slope of the numerical results.The curvature which is evident in the numerical data for k farther from k c is apparently a higher-order effect.Note that the width of the band of ripple solutions increases withǫ,so an appreciably largeǫis required to reach these larger values of|k−k c|.In Figures5a and5b we plot the phase anglesθ2andθ3against k.The agreement between the simulations and the weakly nonlinear analysis is again quite strong for J near onset.The order-ǫterms in the analytical results match the slope of the numerical data.For higher J we observe a systematic15downward deviation in the numerical results.The shift appears to be linear in J,and so is second-order inǫ≡(J−J c)1/2.6DiscussionWe have carried out numerical and weakly nonlinear analyses of the Nishimori-Ouchi continuum model[3,11]for windblown sand,and also for a modifica-tion of that model which respects the physical symmetry of the system under changes of the reference level of height.Both versions of the model yield the surprising result that the ripple patterns,which form when theflat sandbed becomes unstable,drift upwind even as the sand which forms the ripples is blown downwind.This drift is found in the linear stability analysis and persists in the weakly nonlinear results,and numerical integrations confirm that it is a real consequence of the model.Such a counterintuitive result has not been examined or detected by previous Monte Carlo simulations of this model[3,11]or in real experiments[10].It would be interesting to check experimentally whether or not ripples can move against the wind.The sym-metric version of the model actually predicts a considerably higher upwind drift speed than the original Nishimori-Ouchi version.It may also be surprising that the differences between the symmetric and Nishimori-Ouchi models are merely qualitative.The restabilized ripple pattern for a given value of the control parameter have smaller amplitudes (by a factor of about3)and higher drift velocities(by a factor of over5) in the symmetric model than in the original version.The relative sizes and phases of the higher harmonics in the ripple shape are also different for the two models.A number of modifications to the model are needed in order to make it comparable with experiments.A major ingredient that is left out of the model is any effect of the surface topography on the wind.This lack means that there is no shadowing effect in the model.Including such an effect would make it more likely for grains to settle on the downwind side of a ripple than on the upwind side,and more likely for them to be blown offthe upwind side than the downwind side.This would likely reduce the tendency of the ripples to drift upwind.The result that the ripples drift upwind in this model, which neglects shadowing,may be an indirect indication of the importance of shadowing in the development of real ripple patterns.An improved model16of creep may also be needed;a downwind bias in the creep would modify the drift velocity.Perhaps most critical is a better and more realistic form of the saltation function,which must account the effects of the topography of the sandbed,and the many particle dynamics of the grains in the air as well as on the surface.17References[1]R.A.Bagnold,Proc.Roy.Soc.A157,594(1936);See also The physics of blown sand and desert dunes,reprinted by Chapman and Hall(1981). [2]K.Pye and H.Tsoar,Aeolian sand and sand dunes,Unwin Hyman,Lon-don(1990).[3]H.Nishimori and N.Ouchi,Phys.Rev.Lett.71,197(1993).[4]R.S.Anderson,Sedimentology,34,943(1987).[5]O.Terzidis,P.Claudin,and J.P.Bouchaud,cond-matt/9801295.[6]For recent observations of surface instabilities that develop when grains are subject to vibrations,see:F.Melo,P.Umbanhowar,and H.L.Swinney, Phys.Rev.Lett.75,3838(1995);T.H.Metcalf,J.B.Knight,and H.M. Jaeger,Physica A236,202(1997);K.M.Aoki and T.Akiyama,Phys.Rev. Lett.77,4166(1996).[7]See,e.g.:nger,Science243,1150(1989);D.A.Kessler,H.Levine, and J.Koplik,Adv.Phys.37,255(1988);Dynamics of curved fronts,edited by P.Pelce,Academic,San Diego,(1988)and references therein.[8]See,e.g.,M.Ben-Amar and B.Moussallam,Phys.Rev.Lett.60,317 (1989)and references therein.[9]D.A.Kurtze and D.C.Hong,J.Korean.Phys.Soc.28(2),178(1995) and references therein.[10]A.Betat,V.Frette,and I.Rehberg,Phys.Rev.Lett.83,88(1999).[11]More detailed description of the model can be found in:H.Nishimori and N.Ouchi,Int.J.Mod.Phys.B.Vol.7,#9&10,2025(1995).18。