Pilkington浮法玻璃生产介绍.ppt

AmemberofNSGGroup,2,ApplicationofInorganicChemistryinIndustry,FlatGlassandCoatingsOnGlassDrTroyManningAdvancedTechnologist,On-lineCoatingsPilkingtonEuropeanTechnicalCentreHallLaneLathomUKtroy.manning,3,Outline,OverviewofFlatGlassindustryandNSG/PilkingtonFlatGlassmanufactureFloatGlassProcessCoatingtechnologywithintheglassindustryChemicalVapourDepositionExamplesofonlinecoatingapplicationsLowEmissivity/SolarControlSelfCleaningSummarySuggestedReading,4,GlobalFlatGlassMarket,GlobalMarket37milliontonnes(4.4billionsq.m)BuildingProducts33mtonnes-Automotive4mtonnesOfwhich24million=highqualityfloatglass3million=sheet2million=rolled8million=lowerqualityfloat(mostlyChina)GlobalValueAtprimarymanufacturelevel15billionAtprocessedlevel50billion,5,NSGandPilkingtoncombined,AglobalglassleaderthepureplayinFlatGlassCombinedannualsalesc.4billionEqualtoAsahiGlassinscale,mostprofitableinFlatGlassOwnership/interestsin46floatlines6.4milliontonnesannualoutputWidenedAutomotivecustomerbase36,000employeesworldwideManufacturingoperationsin26countriesSalesin130+countries,6,ManufactureofFlatGlass,FourmainmethodsPlateGlass(1688)moltenglasspouredontoaflatbed,spread,cooledandpolishedSheetGlass(1905)continuoussheetofglassdrawnfromtankofmoltenglassRolledGlass(1920)moltenglasspouredontototworollerstoachieveaneventhickness,makingpolishingeasier.Usedtomakepatternedandwiredglass.FloatGlass(1959)moltenglasspouredontobedofmoltentinanddrawnoffincontinuousribbon.Giveshighqualityflatglasswitheventhicknessandfirepolishfinish.320float-glasslinesworldwide,7,Meltingfurnace,Floatbath,Coolinglehr,Continuosribbonofglass,Crosscutters,Largeplatelift-offdevices,Smallplatelift-offdevices,Rawmaterialfeed,TheFloat-GlassProcess,Operatesnon-stopfor10-15years6000km/year0.4mm-25mmthick,upto3mwide,8,TheFloatGlassProcess,9,Rawmaterials,10,MeltingFurnace,11,FloatBath,12,FloatGlassPlant,13,TheFloat-GlassProcess,Fine-grainedingredients,closelycontrolledforquality,aremixedtomakebatch,whichflowsasablanketontomoltenglassat1500Cinthemelter.Thefurnacecontains2000tonnesofmoltenglass.,Afterabout50hours,glassfromthemelterflowsgentlyoverarefractoryspoutontothemirror-likesurfaceofmoltentin,startingat1100Candleavingthefloatbathasasolidribbonat600C.,Despitethetranquillitywithwhichfloatglassisformed,considerablestressesaredevelopedintheribbonasitcools.,14,RawMaterials,Oxide%inglassRawmaterialsourceSiO272.2SandNa2O13.4SodaAsh(Na2CO3)CaO8.4Limestone(CaCO3)MgO4.0Dolomite(MgCO3.CaCO3)Al2O31.0Impurityinsand,FeldsparorCalumiteFe2O30.11ImpurityinsandorRouge(Fe2O3)SO30.20SodiumsulphateC0.00Anthracite,15,Rawmaterials,SiO2Verydurable,BUThighmeltingpoint(1700C)!+Na2OMeltsatalowertemperature,BUTdissolvesinwater!+CaOMoredurable,BUTwillnotforminbathwithoutcrystallisation+MgOGlassstaysasasuper-cooledliquidinbath,nocrystallisation+Al2O3Addsdurability+Fe2O3Addsrequiredlevelofgreencolourforcustomer,16,ChemistryofGlass,Importantglassmakingchemistry:basicreactionsNa2CO3+SiO21500CNa2SiO3+CO2Na2SiO3+xSiO2Na2SO4(Na2O)(SiO2)(x+1),Digestion,17,CompositionofGlass,18,StructureofGlass,RandomnetworkofSiO4-tetrahedralunits.Na-OenterSi-OnetworkaccordingtovalencyNetworkFormersCaandMgNetworkModifiersmakestructuremorecomplextopreventcrystallisation,19,Body-tintedGlass,20,CIELa*b*colourspace,21,CIELa*b*colourspace,22,FunctionsofaWindow,Lightinhomes,officesLightoutshops,museumdisplaysHeatinheatingdominatedclimatesHeatoutcoolingdominatedclimatesCanchangepropertiesofglassbyapplyingcoatingstothesurface,23,Makingawindowfunctional-coatings,AwidevarietyofcoatingtechnologiesareutilisedbytheglassindustrySprayPyrolysisPowderSprayChemicalVapourDepositionSputterCoatingThermalEvaporationCoatingsSolGelCoatingsTheseareappliedOnLinei.e.astheglassisproducedonthefloatlineOffLinei.e.coatingnotnecessarilyproducedatthesamelocation,24,VariationsofCVD,AtmosphericPressureAPCVDLowPressure-LPCVDAerosolAssisted-AACVDMetalorganicMOCVDCombustion/FlameCCVDHotWire/FilamentHWCVD/HFCVDPlasmaEnhanced-PECVDLaserAssistedLACVDMicrowaveAssistedMWCVDAtomicLayerDepositionALD,25,ChemicalVapourDeposition,26,ChemicalVapourDeposition,Maingasflowregion,GasPhaseReactions,SurfaceDiffusion,DesorptionofFilmPrecursor,ByProducts,Diffusiontosurface,27,ChemicalVapourDeposition,AnimationkindlysuppliedbyDr.WarrenCross,UniversityofNottingham,28,CVDprocessesandparameters,29,CVDPrecursorProperties,Volatilegas,liquid,lowmeltingpointsolid,sublimablesolidPureStableundertransportReact/DecomposecleanlytogivedesiredcoatingminimisecontaminantsCanbesinglesourceordual/multi-source,30,CVDPrecursors,SingleSourcepyrolysis(thermaldecomposition)e.gTi(OC2H5)4TiO2+4C2H4+2H2O(400C)Oxidatione.gSiH4(g)+O2(g)SiO2(s)+2H2(g)Reductione.g.WF6(g)+3H2(g)W(s)+6HF(g)Dualsourcee.g.TiCl4(g)+4EtOH(g)TiO2(s)+4HCl(g)+2EtOEt(g),31,DualSourceandSingleSourcePrecursors,32,TransportofPrecursors,Bubblerforliquidsandlowmeltingsolids,DirectLiquidInjectionsyringeandsyringedriverforliquidsandsolutionsSublimationforsolidshotgaspassedoverheatedprecursorAerosolofprecursorsolutions,33,EffectofTemperatureonGrowthRate,Independentoftemperature,34,Flowconditions,LaminarFlowregime,TurbulentFlowRegime,35,ReynoldsNumber,Dimensionlessnumberdescribingflowconditions,r=Massdensityrelatedtoconcnandpartialpressureu=averagevelocity=viscosityL=relevantlength,relatedtoreactordimensions,IfRe1000fullyturbulentflowRealityisbetweenthetwoextremes,36,DimensionlessNumbers,ReducesthenumberofparametersthatdescribeasystemMakesiteasiertodeterminerelationshipsexperimentallyForexample:DragForceonaSphereVariables:Force=f(velocity,diameter,viscosity,density)Canbereducedto2“dimensionlessgroups”:Dragcoefficient(CD)andReynoldsnumber(Re),37,DimensionlessNumbers,Laminarflowregime,Turbulentflowregime,ExperimentalvaluesofCDforspheresinfluidflowsatvariousRe,38,BoundaryLayergasvelocity,Frictionalforcesagainstreactorwallsdecreasegasvelocity,Theboundarylayerthicknesscanbeestimatedfrom:,39,BoundaryLayer-temperature,Contactwithhotsurfacesincreasestemperature,40,BoundaryLayerprecursorconcentration,Depletionofprecursordecreasesgasphaseconcentration,41,NucleationandGrowth,VanderWaalstypeadsorptionofprecursortosubstrate,Precursorsthendiffuseacrosssurface,Precursorsdiffuseacrossboundarylayertosurface,Andcanbedesorbedbackintomaingasflow,Orcanfindlowenergybindingsitestocoalesceintofilm,MainGasFlow,42,NucleationandGrowth,43,GrowthMechanisms,(b)Frank-vanderMerwe,Layergrowth,(c)Stranski-Kastanov,Mixedlayeredandisland,growth,(a)Volmer-Weber,Islandgrowth,44,ThinFilmAnalysis,ManytechniquesareusedtocharacterisethinfilmsExamplesincludeXRDcrystallinity,phaseXRRlayerthickness,layerroughnessSEM/EDX/WDXmorphology,thickness,compositionRamanphase,bondingFTIRphase,bondingXPScomposition,depthprofiling,dopingSIMScomposition,depthprofiling,dopingAFMroughness,surfacemorphologyTEMcrystallinestructure,crystaldefectsAnalysisoffunctionalproperties,45,CVDonGlass,Foron-linecoatingofglasswerequire:Highgrowthratesrequiredthicknessin100nm/spossibleLowprecursorefficiency10%,SiCxOy(70nm),SnO2:F(350nm),Glass,SiH4+C2H4+CO2SiCxOy+H2O+otherby-productsUsedascoloursuppressionandbarrierlayer,58,LowEmissivityCoating,GenerallybasedonSnO2:F(TransparentConductiveOxide)SiCOunderlayerusedascoloursuppressant,59,Low-EandSolarControlCoatings,60,Self-CleaningGlass,Twomechanisms:SuperhydrophilicityPhotocatalyticdegradationoforganicmatter.TiO2coating,61,Superhydrophilicity,Oxygenvacancies,O,H,O,O,O,O,H,H,H,2,O,(,O,H,-,H,+,),Waterdroplets,Uniformwaterfilm,UVilluminationtime,Contactangle,o,o,o,o,o,o,o,dark,UV,62,PhotocatalyticActivity,UltrabandgapirradiationofTiO2GenerationofelectronholeinvalencebandHolemigratestothesurfaceandresultsinoxidationoforganicmaterial,63,Semi-conductorPhotocatalysis,A.Mills,SLeHunte,J.Photochem.PhotobiolA,1997,108,1-35.,64,CVDofActivTM,SiO2(30nm),TiO2(17nm),Glass,SiH4+O2+C2H4SiO2+by-productsUsedasbarrierlayertopreventdiffusionofNaionsintoTiO2layer,TiCl4+EtOAcTiO2+HCl+organicby-products,LaminarFlowregimeReasonablegrowthratesandprecursorefficiency,65,ActivTM,66,ActivTM,67,ActivTM,68,Superhydrophilicity,15minsUVExposure,30minsUVExposure,45minsUVExposure,BeforeUVExposure,69,PhotocatalyticEffect,UV-AbsorptionO2-OH*,OrganicSoil,H2O+CO2,Glass,BarrierLayer,TiO2-Layer,70,PhotocatalyticEffect,Thephotoactivityofthecoatingcanbemeasuredbymonitori