Pilkington浮法玻璃生产介绍课件

AmemberofNSGGroup1AmemberofNSGGroup1ApplicationofInorganicChemistryinIndustryFlatGlassandCoatingsOnGlassDrTroyManningAdvancedTechnologist,On-lineCoatingsPilkingtonEuropeanTechnicalCentreHallLaneLathomUKtroy.manningpilkington2ApplicationofInorganicChemiOutlineOverviewofFlatGlassindustryandNSG/PilkingtonFlatGlassmanufacture FloatGlassProcessCoatingtechnologywithintheglassindustryChemicalVapourDepositionExamplesofonlinecoatingapplicationsLowEmissivity/SolarControlSelfCleaningSummarySuggestedReading3OutlineOverviewofFlatGlassGlobalFlatGlassMarketGlobalMarket

37milliontonnes(4.4billionsq.m)BuildingProducts33mtonnes-Automotive4mtonnesOfwhich24million=highqualityfloatglass3million=sheet2million=rolled8million=lowerqualityfloat(mostlyChina)

GlobalValue

Atprimarymanufacturelevel€15billionAtprocessedlevel€50billion4GlobalFlatGlassMarketGlobalNSGandPilkingtoncombinedAglobalglassleader–thepureplayinFlatGlassCombinedannualsalesc.£4billionEqualtoAsahiGlassinscale,mostprofitableinFlatGlassOwnership/interestsin46floatlines6.4milliontonnesannualoutputWidenedAutomotivecustomerbase36,000employeesworldwideManufacturingoperationsin26countriesSalesin130+countries5NSGandPilkingtoncombinedAgManufactureofFlatGlassFourmainmethodsPlateGlass(1688)–moltenglasspouredontoaflatbed,spread,cooledandpolishedSheetGlass(1905)–continuoussheetofglassdrawnfromtankofmoltenglassRolledGlass(1920)–moltenglasspouredontototworollerstoachieveaneventhickness,makingpolishingeasier.Usedtomakepatternedandwiredglass.FloatGlass(1959)–moltenglasspouredontobedofmoltentinanddrawnoffincontinuousribbon.Giveshighqualityflatglasswitheventhicknessandfirepolishfinish.~320float-glasslinesworldwide6ManufactureofFlatGlassFourMeltingfurnaceFloatbathCoolinglehrContinuosribbonofglassCrosscuttersLargeplatelift-offdevicesSmallplatelift-offdevicesRawmaterialfeedTheFloat-GlassProcessOperatesnon-stopfor10-15years6000km/year0.4mm-25mmthick,upto3mwide7MeltingfurnaceFloatbathCooliTheFloatGlassProcess8TheFloatGlassProcess8Rawmaterials9Rawmaterials9MeltingFurnace10MeltingFurnace10FloatBath11FloatBath11FloatGlassPlant12FloatGlassPlant12TheFloat-GlassProcessFine-grainedingredients,closelycontrolledforquality,aremixedtomakebatch,whichflowsasablanketontomoltenglassat1500ºCinthemelter.Thefurnacecontains2000tonnesofmoltenglass.Afterabout50hours,glassfromthemelterflowsgentlyoverarefractoryspoutontothemirror-likesurfaceofmoltentin,startingat1100ºCandleavingthefloatbathasasolidribbonat600ºC.Despitethetranquillitywithwhichfloatglassisformed,considerablestressesaredevelopedintheribbonasitcools.13TheFloat-GlassProcessFine-grRawMaterialsOxide %inglassRawmaterialsourceSiO2 72.2 SandNa2O 13.4 SodaAsh(Na2CO3)CaO 8.4 Limestone(CaCO3)MgO 4.0 Dolomite(MgCO3.CaCO3)Al2O3 1.0 Impurityinsand,FeldsparorCalumiteFe2O3 0.11 ImpurityinsandorRouge(Fe2O3)SO3 0.20 SodiumsulphateC 0.00 Anthracite14RawMaterialsOxide %inglRawmaterials

SiO2 Verydurable,BUThighmeltingpoint(>1700°C)!+Na2O Meltsatalowertemperature,BUTdissolvesinwater!+CaO Moredurable,BUTwillnotforminbathwithout crystallisation+MgO Glassstaysasasuper-cooledliquidinbath,no crystallisation+Al2O3 Addsdurability+Fe2O3 Addsrequiredlevelof‘green’colourforcustomer15RawmaterialsSiO2 VerydurablChemistryofGlassImportantglassmakingchemistry:basicreactionsNa2CO3+SiO2

1500ºCNa2SiO3+CO2Na2SiO3+xSiO2

Na2SO4(Na2O)(SiO2)(x+1)Digestion16ChemistryofGlassImportantglCompositionofGlass17CompositionofGlass17StructureofGlassRandomnetworkof[SiO4]-tetrahedralunits.Na-OenterSi-Onetworkaccordingtovalency–NetworkFormersCaandMg–NetworkModifiers–makestructuremorecomplextopreventcrystallisation18StructureofGlassRandomnetwoBody-tintedGlassIonResultingColourofGlassFerrous(Fe2+)BlueFerric(Fe3+)YellowFe2++Fe3+GreenSelenium(SeO2)BronzeCobalt(Co2+)Grey/BlueNickel(Ni2+)Grey19Body-tintedGlassIonResultingCIELa*b*colourspace20CIELa*b*colourspace20CIELa*b*colourspace21CIELa*b*colourspace21FunctionsofaWindowLightin–homes,officesLightout–shops,museumdisplaysHeatin–heatingdominatedclimatesHeatout–coolingdominatedclimatesCanchangepropertiesofglassbyapplyingcoatingstothesurface22FunctionsofaWindowLightinMakingawindowfunctional-coatingsAwidevarietyofcoatingtechnologiesareutilisedbytheglassindustrySprayPyrolysisPowderSprayChemicalVapourDepositionSputterCoatingThermalEvaporationCoatingsSolGelCoatings

TheseareappliedOnLinei.e.astheglassisproducedonthefloatlineOffLinei.e.coatingnotnecessarilyproducedatthesamelocation23Makingawindowfunctional-cVariationsofCVDAtmosphericPressure–APCVDLowPressure-LPCVDAerosolAssisted-AACVDMetalorganic–MOCVDCombustion/Flame–CCVDHotWire/Filament–HWCVD/HFCVDPlasmaEnhanced-PECVDLaserAssisted–LACVDMicrowaveAssisted–MWCVDAtomicLayerDeposition–ALD24VariationsofCVDAtmosphericPChemicalVapourDeposition25ChemicalVapourDeposition25ChemicalVapourDepositionMaingasflowregionGasPhaseReactionsSurfaceDiffusionDesorptionofFilmPrecursorByProductsDiffusiontosurface26ChemicalVapourDepositionMainChemicalVapourDepositionAnimationkindlysuppliedbyDr.WarrenCross,UniversityofNottingham27ChemicalVapourDepositionAnimCVDprocessesandparametersProcessParametersTransportPrecursorsGasphasereactionPressure,temperature,flowconditions,boundarylayerthickness,gasphaseconcentration,precursors,carriergasDiffusionPressure,temperature,flowconditions,boundarylayerthickness,gasphaseconcentrationAdsorptionTemperature,gasphaseconcentration,numberandnatureofsitesSurfacereactionTemperature,natureofsurfaceDesorptionofby-productsTemperature,pressure,natureofsurfaceDiffusiontolatticesiteTemperature,surfacemobility,numberofvacantsites28CVDprocessesandparametersPrCVDPrecursorPropertiesVolatile–gas,liquid,lowmeltingpointsolid,sublimablesolidPureStableundertransportReact/Decomposecleanlytogivedesiredcoating–minimisecontaminantsCanbesinglesourceordual/multi-source29CVDPrecursorPropertiesVolatiCVDPrecursorsSingleSource–pyrolysis(thermaldecomposition)e.gTi(OC2H5)4TiO2+4C2H4+2H2O(>400ºC)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)30CVDPrecursorsSingleSource–DualSourceandSingleSourcePrecursorsFilmDualSourceSingleSourceGaAsGaCl3+AsH3Me2Ga(AsH2)TiNTiCl4+NH3Ti(NMe2)4WSiWCl6+SiH4W(SiR)4TiO2TiCl4+H2OTi(OiPr)4CdSeCdMe2+H2SeCd(SeR)231DualSourceandSingleSourceTransportofPrecursorsBubblerforliquidsandlowmeltingsolidsDirectLiquidInjection–syringeandsyringedriverforliquidsandsolutionsSublimationforsolids–hotgaspassedoverheatedprecursorAerosolofprecursorsolutions32TransportofPrecursorsBubblerEffectofTemperatureonGrowthRateIndependentoftemperature33EffectofTemperatureonGrowtFlowconditionsLaminarFlowregimeTurbulentFlowRegime34FlowconditionsLaminarFlowreReynoldsNumberDimensionlessnumberdescribingflowconditionsr=Massdensityrelatedtoconcnandpartialpressureu=averagevelocity=viscosityL=relevantlength,relatedtoreactordimensionsIfRe<10LaminarflowIfRe>>1000fullyturbulentflowRealityisbetweenthetwoextremes35ReynoldsNumberDimensionlessnDimensionlessNumbersReducesthenumberofparametersthatdescribeasystemMakesiteasiertodeterminerelationshipsexperimentallyForexample:DragForceonaSphere Variables:Force=f(velocity,diameter,viscosity,density)Canbereducedto2“dimensionlessgroups”: Dragcoefficient(CD)andReynoldsnumber(Re)36DimensionlessNumbersReducestDimensionlessNumbersLaminarflowregimeTurbulentflowregimeExperimentalvaluesofCDforspheresinfluidflowsatvariousRe37DimensionlessNumbersLaminarfBoundaryLayer–gasvelocityFrictionalforcesagainstreactorwallsdecreasegasvelocityTheboundarylayerthicknesscanbeestimatedfrom:38BoundaryLayer–gasvelocityFBoundaryLayer-temperatureContactwithhotsurfacesincreasestemperature39BoundaryLayer-temperatureCoBoundaryLayer–precursorconcentrationDepletionofprecursordecreasesgasphaseconcentration40BoundaryLayer–precursorconNucleationandGrowthVanderWaalstypeadsorptionofprecursortosubstratePrecursorsthendiffuseacrosssurfacePrecursorsdiffuseacrossboundarylayertosurfaceAndcanbedesorbedbackintomaingasflowOrcanfindlowenergybindingsitestocoalesceintofilmMainGasFlow41NucleationandGrowthVanderWNucleationandGrowthSubstrateTemperatureGrowthRateSurfaceDiffusionCrystallinityLowHighSlowrelativefluxofprecursorsAmorphous–nocrystallinestructureHighLowFastrelativetofluxofprecursorsEpitaxial–replicatessubstratestructureIntermediateIntermediateIntermediatePolycrystalline42NucleationandGrowthSubstrateGrowthMechanisms(b)Frank-vanderMerweLayergrowth(c)Stranski-KastanovMixedlayeredandislandgrowth(a)Volmer-WeberIslandgrowth43GrowthMechanisms(b)Frank-vThinFilmAnalysisManytechniquesareusedtocharacterisethinfilmsExamplesincludeXRD–crystallinity,phaseXRR–layerthickness,layerroughnessSEM/EDX/WDX–morphology,thickness,compositionRaman–phase,bondingFTIR–phase,bondingXPS–composition,depthprofiling,dopingSIMS–composition,depthprofiling,dopingAFM–roughness,surfacemorphologyTEM–crystallinestructure,crystaldefectsAnalysisoffunctionalproperties44ThinFilmAnalysisManytechniqCVDonGlassForon-linecoatingofglasswerequire:Highgrowthrates–requiredthicknessin<2sStablechemistry–uniformcoatingsforcontinuousoperationformanydaysGoodadhesiontoglassHighefficiency–reducecosts45CVDonGlassForon-linecoatinAPCVDStrengthsandWeaknessesStrengthsWeaknessesResultOn-linecoatingpossibleReducedflexibilityReducedlabourcosts,highvolumemanufactureFreshsubstratesurfacesNowashingstep,enhancedadhesionHighdepositionratesNeedtomatchlinespeedThickfilmspossiblewithhighthroughputHardfilmsImprovedprocessabilityandperformanceStructurecontrolpossiblee.g.crystallinityRoughsurfaceImprovedfunctionalpropertiesanddurabilityVolatileprecursorsrequiredLimitedrangeofmaterials46APCVDStrengthsandWeaknessesOn-LineCoatingPositionsLoadrawmaterialsMeltingFloatingCoolingCuttingandStacking25ºCGlassribbon600ºC1050ºC40ºC1500ºCPossiblepositionsforCVDcoatingsystems47On-LineCoatingPositionsLoadLaminarFlowCVDCoaterGlassGlassRibbonFlowUp-StreamExhaustDown-StreamExhaustPrecursorgasesOutsideAtmosphere48LaminarFlowCVDCoaterGlassGlAPCVDApplicationsonGlassCoatingtechnologyallowsustoaddfunctionalitytoglassCoatingtechnologyistodayusedforavarietyofproductsLowEmissivitycoatingstoreduceheatingbillsSolarControlcoatingstoreducesolarheatgainTechnicalproductse.g.TCO’sforLCDdisplays,solarcellsAnti-ReflectiveProductsHydrophobicCoatingsSelfCleaningCoatingsSmartCoatingse.g.electrochromics,thermochromics,photochromics49APCVDApplicationsonGlassCoaLow-EmissivityCoatingsDesignedtoreduceheatingbillsInadoubleglazedunit,alow-emissivitycoatingontheinnerpaneblocksradiativeheattryingtoescapeintothecavity50Low-EmissivityCoatingsDesigneEmissivityEmissivityistheratioofradiationemittedbyablackbodyorasurfacetothetheoreticalradiationpredictedbyPlanck’slaw.Surfaceemissivityisgenerallymeasuredindirectlybyassumingthate

=

1

-

reflectivity,usuallyataspecifiedwavelength51EmissivityEmissivityistheraSolarSpectrumWehavetodistinguishbetween:whatcomesfromtheoutsidetotheinside–solarspectrumwhatgoesfromtheinsidetotheoutside-heatVisiblelightInfra-RedUV52SolarSpectrumWehavetodistiOutsidetoInsideOptimalcurveforsolarcontrol-noUV -allvisiblelightpass -noIROptimalcurveforlow-e-noUV -allvisiblelightpass -allIRpass53OutsidetoInsideOptimalcurveInsidetoOutside–NoGlazing5µm50µmHeatradiation(“Blackbody”)at23.9ºC

UVVisiblelightIR54InsidetoOutside–NoGlazingInsidetoOutside–Low-eCoatedGlassLowemissivitycoatedproductslimittheblackbodyradiationi.e.theenergylossesthroughthewindow: K-Glasse=0.1555InsidetoOutside–Low-eCoatTransparentConductingOxidesDopedmetaloxidesdisplayingn-typeconductivityF-substitutesforO2-intheSnO2latticereleasinganelectronintotheconductionbandi.e.Sn4+O2-2-xF-xe-xClosetometallicconductivity(15W/€)canbeachievedbutwithhighopticaltransmittance(bandgap~4eV)C.G.Granqvist,Adv.Mater.,2019,15,1789-180356TransparentConductingOxidesDCVDofSnO2:FSnCl4+H2O+HFSnO2:F+HCl(~1.5at%F)MuchgasphasereactionGasesintroducedseparatelyinturbulentflowregimeVeryhighgrowthrates>100nm/spossibleLowprecursorefficiency<10%SiCxOy(70nm)SnO2:F(350nm)GlassSiH4+C2H4+CO2

SiCxOy+H2O+otherby-productsUsedascoloursuppressionandbarrierlayer57CVDofSnO2:FSnCl4+H2O+HFLowEmissivityCoatingGenerallybasedonSnO2:F(TransparentConductiveOxide)SiCOunderlayerusedascoloursuppressant58LowEmissivityCoatingGenerallLow-EandSolarControlCoatings59Low-EandSolarControlCoatinSelf-CleaningGlassTwomechanisms:SuperhydrophilicityPhotocatalyticdegradationoforganicmatter.TiO2coating60Self-CleaningGlassTwomechaniSuperhydrophilicityOxygenvacanciesTiO-TiOTiHTiTiTiH+TiOTiOTiTiOTiOTiHHH2O(OH-,

H+)WaterdropletsUniformwaterfilmUVilluminationtimeContactangleooooooodarkUV61SuperhydrophilicityOxygenvacaPhotocatalyticActivityUltrabandgapirradiationofTiO2

GenerationofelectronholeinvalencebandHolemigratestothesurfaceandresultsinoxidationoforganicmaterialValence

BandConductance

BandOxidationReductionAA+BB-h+hn62PhotocatalyticActivityUltrabSemi-conductorPhotocatalysisA.Mills,SLeHunte,J.Photochem.PhotobiolA,2019,108,1-35.63Semi-conductorPhotocatalysisACVDofActivTMSiO2(30nm)TiO2(17nm)GlassSiH4+O2+C2H4

SiO2+by-productsUsedasbarrierlayertopreventdiffusionofNaionsintoTiO2layerTiCl4+EtOAcTiO2+HCl+organicby-productsLaminarFlowregimeReasonablegrowthratesandprecursorefficiency64CVDofActivTMSiO2(30nm)TiO2ActivTM65ActivTM65ActivTM66ActivTM66ActivTM67ActivTM67Superhydrophilicity15minsUVExposure30minsUVExposure45minsUVExposureBeforeUVExposure68Superhydrophilicity15minsUVPhotocatalyticEffect

UV-AbsorptionO2-OH*OrganicSoilH2O+CO2GlassBarrierLayerTiO2-Layer69PhotocatalyticEffectUV-AbsoPhotocatalyticEffectThephotoactivityofthecoatingcanbemeasuredbymonitoringthedecompositionofastandardcontaminantAthinfilmofstearicacid(n-octadecanoicacid,~200Å)isappliedfromamethanolsolutionontothecoatingStearicacidusedasatypicalorganiccontaminantFTIR(Fouriertransforminfra-redspectroscopy)usedtodetectC-HstretchofstearicacidC-HabsorptionintensitymeasuredaftervaryingUVexposure70PhotocatalyticEffectThephotoStearicAcidDecompositionC-HAbsorptionZeroUVexposureC-HAbsorption~60minsUVexposureUV0.77W/m2340nm71StearicAcidDecompositionC-HPilkingtonActivTM72PilkingtonActivTM72SummaryScaleoftheGlobalFlatGlassIndustryManufacturingFlatGlass–FloatGlassProcessCoatingGlass–ChemicalVapourDepositionExamplesofcommercialglazingcoatingspreparedbyCVD73SummaryScaleoftheGlobalFlaRecommendedReadingD.W.SheelandM.E.PembleAtmosphericPressureCVDCoatingsonGlass,ICCG42019

cvdtechnologies.co.uk/CVD%20on%20Glass.pdfM.L.Hitchman,K.F.JensenChemicalVaporDepositionAcademicPress,1993W.S.Rees,CVDofNon-metals,VCH,Weinheim,2019M.OhringTheMaterialsScienceofThinFilms,AcademicPress,2019pilkington74RecommendedReadingD.W.SheelFirstinGlass™75FirstinGlass™75谢谢你的阅读知识就是财富丰富你的人生谢谢你的阅读知识就是财富AmemberofNSGGroup77AmemberofNSGGroup1ApplicationofInorganicChemistryinIndustryFlatGlassandCoatingsOnGlassDrTroyManningAdvancedTechnologist,On-lineCoatingsPilkingtonEuropeanTechnicalCentreHallLaneLathomUKtroy.manningpilkington78ApplicationofInorganicChemiOutlineOverviewofFlatGlassindustryandNSG/PilkingtonFlatGlassmanufacture FloatGlassProcessCoatingtechnologywithintheglassindustryChemicalVapourDepositionExamplesofonlinecoatingapplicationsLowEmissivity/SolarControlSelfCleaningSummarySuggestedReading79OutlineOverviewofFlatGlassGlobalFlatGlassMarketGlobalMarket

37milliontonnes(4.4billionsq.m)BuildingProducts33mtonnes-Automotive4mtonnesOfwhich24million=highqualityfloatglass3million=sheet2million=rolled8million=lowerqualityfloat(mostlyChina)

GlobalValue

Atprimarymanufacturelevel€15billionAtprocessedlevel€50billion80GlobalFlatGlassMarketGlobalNSGandPilkingtoncombinedAglobalglassleader–thepureplayinFlatGlassCombinedannualsalesc.£4billionEqualtoAsahiGlassinscale,mostprofitableinFlatGlassOwnership/interestsin46floatlines6.4milliontonnesannualoutputWidenedAutomotivecustomerbase36,000employeesworldwideManufacturingoperationsin26countriesSalesin130+countries81NSGandPilkingtoncombinedAgManufactureofFlatGlassFourmainmethodsPlateGlass(1688)–moltenglasspouredontoaflatbed,spread,cooledandpolishedSheetGlass(1905)–continuoussheetofglassdrawnfromtankofmoltenglassRolledGlass(1920)–moltenglasspouredontototworollerstoachieveaneventhickness,makingpolishingeasier.Usedtomakepatternedandwiredglass.FloatGlass(1959)–moltenglasspouredontobedofmoltentinanddrawnoffincontinuousribbon.Giveshighqualityflatglasswitheventhicknessandfirepolishfinish.~320float-glasslinesworldwide82ManufactureofFlatGlassFourMeltingfurnaceFloatbathCoolinglehrContinuosribbonofglassCrosscuttersLargeplatelift-offdevicesSmallplatelift-offdevicesRawmaterialfeedTheFloat-GlassProcessOperatesnon-stopfor10-15years6000km/year0.4mm-25mmthick,upto3mwide83MeltingfurnaceFloatbathCooliTheFloatGlassProcess84TheFloatGlassProcess8Rawmaterials85Rawmaterials9MeltingFurnace86MeltingFurnace10FloatBath87FloatBath11FloatGlassPlant88FloatGlassPlant12TheFloat-GlassProcessFine-grainedingredients,closelycontrolledforquality,aremixedtomakebatch,whichflowsasablanketontomoltenglassat1500ºCinthemelter.Thefurnacecontains2000tonnesofmoltenglass.Afterabout50hours,glassfromthemelterflowsgentlyoverarefractoryspoutontothemirror-likesurfaceofmoltentin,startingat1100ºCandleavingthefloatbathasasolidribbonat600ºC.Despitethetranquillitywithwhichfloatglassisformed,considerablestressesaredevelopedintheribbonasitcools.89TheFloat-GlassProcessFine-grRawMaterialsOxide %inglassRawmaterialsourceSiO2 72.2 SandNa2O 13.4 SodaAsh(Na2CO3)CaO 8.4 Limestone(CaCO3)MgO 4.0 Dolomite(MgCO3.CaCO3)Al2O3 1.0 Impurityinsand,FeldsparorCalumiteFe2O3 0.11 ImpurityinsandorRouge(Fe2O3)SO3 0.20 SodiumsulphateC 0.00 Anthracite90RawMaterialsOxide %inglRawmaterials

SiO2 Verydurable,BUThighmeltingpoint(>1700°C)!+Na2O Meltsatalowertemperature,BUTdissolvesinwater!+CaO Moredurable,BUTwillnotforminbathwithout crystallisation+MgO Glassstaysasasuper-cooledliquidinbath,no crystallisation+Al2O3 Addsdurability+Fe2O3 Addsrequiredlevelof‘green’colourforcustomer91RawmaterialsSiO2 VerydurablChemistryofGlassImportantglassmakingchemistry:basicreactionsNa2CO3+SiO2

1500ºCNa2SiO3+CO2Na2SiO3+xSiO2

Na2SO4(Na2O)(SiO2)(x+1)Digestion92ChemistryofGlassImportantglCompositionofGlass93CompositionofGlass17StructureofGlassRandomnetworkof[SiO4]-tetrahedralunits.Na-OenterSi-Onetworkaccordingtovalency–NetworkFormersCaandMg–NetworkModifiers–makestructuremorecomplextopreventcrystallisation94StructureofGlassRandomnetwoBody-tintedGlassIonResultingColourofGlassFerrous(Fe2+)BlueFerric(Fe3+)YellowFe2++Fe3+GreenSelenium(SeO2)BronzeCobalt(Co2+)Grey/BlueNickel(Ni2+)Grey95Body-tintedGlassIonResultingCIELa*b*colourspace96CIELa*b*colourspace20CIELa*b*colourspace97CIELa*b*colourspace21FunctionsofaWindowLightin–homes,officesLightout–shops,museumdisplaysHeatin–heatingdominatedclimatesHeatout–coolingdominatedclimatesCanchangepropertiesofglassbyapplyingcoatingstothesurface98FunctionsofaWindowLightinMakingawindowfunctional-coatingsAwidevarietyofcoatingtechnologiesareutilisedbytheglassindustrySprayPyrolysisPowderSprayChemicalVapourDepositionSputterCoatingThermalEvaporationCoatingsSolGelCoatings

TheseareappliedOnLinei.e.astheglassisproducedonthefloatlineOffLinei.e.coatingnotnecessarilyproducedatthesamelocation99Makingawindowfunctional-cVariationsofCVDAtmosphericPressure–APCVDLowPressure-LPCVDAerosolAssisted-AACVDMetalorganic–MOCVDCombustion/Flame–CCVDHotWire/Filament–HWCVD/HFCVDPlasmaEnhanced-PECVDLaserAssisted–LACVDMicrowaveAssisted–MWCVDAtomicLayerDeposition–ALD100VariationsofCVDAtmosphericPChemicalVapourDeposition101ChemicalVapourDeposition25ChemicalVapourDepositionMaingasflowregionGasPhaseReactionsSurfaceDiffusionDesorptionofFilmPrecursorByProductsDiffusiontosurface102ChemicalVapourDepositionMainChemicalVapourDepositionAnimationkindlysuppliedbyDr.WarrenCross,UniversityofNottingham103ChemicalVapourDepositionAnimCVDprocessesandparametersProcessParametersTransportPrecursorsGasphasereactionPressure,temperature,flowconditions,boundarylayerthickness,gasphaseconcentration,precursors,carriergasDiffusionPressure,temperature,flowconditions,boundarylayerthickness,gasphaseconcentrationAdsorptionTemperature,gasphaseconcentration,numberandnatureofsitesSurfacereactionTemperature,natureofsurfaceDesorptionofby-productsTemperature,pressure,natureofsurfaceDiffusiontolatticesiteTemperature,surfacemobility,numberofvacantsites104CVDprocessesandparametersPrCVDPrecursorPropertiesVolatile–gas,liquid,lowmeltingpointsolid,sublimablesolidPureStableundertransportReact/Decomposecleanlytogivedesiredcoating–minimisecontaminantsCanbesinglesourceordual/multi-source105CVDPrecursorPropertiesVolatiCVDPrecursorsSingleSource–pyrolysis(thermaldecomposition)e.gTi(OC2H5)4TiO2+4C2H4+2H2O(>400ºC)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)106CVDPrecursorsSingleSource–DualSourceandSingleSourcePrecursorsFilmDualSourceSingleSourceGaAsGaCl3+AsH3Me2Ga(AsH2)TiNTiCl4+NH3Ti(NMe2)4WSiWCl6+SiH4W(SiR)4TiO2TiCl4+H2OTi(OiPr)4CdSeCdMe2+H2SeCd(SeR)2107DualSourceandSingleSourceTransportofPrecursorsBubblerforliquidsandlowmeltingsolidsDirectLiquidInjection–syringeandsyringedriverforliquidsandsolutionsSublimationforsolids–hotgaspassedoverheatedprecursorAerosolofprecursorsolutions108TransportofPrecursorsBubblerEffectofTemperatureonGrowthRateIndependentoftemperature109EffectofTemperatureonGrowtFlowconditionsLaminarFlowregimeTurbulentFlowRegime110FlowconditionsLaminarFlowreReynoldsNumberDimensionlessnumberdescribingflowconditionsr=Massdensityrelatedtoconcnandpartialpressureu=averagevelocity=viscosityL=relevantlength,relatedtoreactordimensionsIfRe<10LaminarflowIfRe>>1000fullyturbulentflowRealityisbetweenthetwoextremes111ReynoldsNumberDimensionlessnDimensionlessNumbersReducesthenumberofparametersthatdescribeasystemMakesiteasiertodeterminerelationshipsexperimentallyForexample:DragForceonaSphere Variables:Force=f(velocity,diameter,viscosity,density)Canbereducedto2“dimensionlessgroups”: Dragcoefficient(CD)andReynoldsnumber(Re)112DimensionlessNumbersReducestDimensionlessNumbersLaminarflowregimeTurbulentflowregimeExperimentalvaluesofCDforspheresinfluidflowsatvariousRe113DimensionlessNumbersLaminarfBoundaryLayer–gasvelocityFrictionalforcesagainstreactorwallsdecreasegasvelocityTheboundarylayerthicknesscanbeestimatedfrom:114BoundaryLayer–gasvelocityFBoundaryLayer-temperatureContactwithhotsurfacesincreasestemperature115BoundaryLayer-temperatureCoBoundaryLayer–precursorconcentrationDepletionofprecursorde