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1、1Application of Inorganic Chemistry in IndustryFlat Glass and Coatings On GlassDr Troy ManningAdvanced Technologist,On-line CoatingsPilkington European Technical CentreHall LaneLathomUK第1页/共75页2OutlineOverviewofFlatGlassindustryandNSG/PilkingtonFlatGlassmanufactureFloatGlassProcessCoatingtechnologyw
2、ithintheglassindustryChemicalVapourDepositionExamplesofonlinecoatingapplicationsLowEmissivity/SolarControlSelfCleaningSummarySuggestedReading第2页/共75页3Global Flat Glass MarketGlobal Market 37 million tonnes(4.4 billion sq.m)Building Products 33 m tonnes-Automotive 4m tonnesOf which24 million =high qu
3、ality float glass3 million =sheet2 million =rolled8 million =lower quality float(mostly China)Global Value At primary manufacture level 15 billionAt processed level 50 billion第3页/共75页4NSG and Pilkington combinedAglobalglassleaderthepureplayinFlatGlassCombinedannualsalesc.4billionEqualtoAsahiGlassins
4、cale,mostprofitableinFlatGlassOwnership/interestsin46floatlines6.4milliontonnesannualoutputWidenedAutomotivecustomerbase36,000employeesworldwideManufacturingoperationsin26countriesSalesin130+countries第4页/共75页5Manufacture of Flat GlassFour main methodsPlate Glass(1688)molten glass poured on to a flat
5、 bed,spread,cooled and polishedSheet Glass(1905)continuous sheet of glass drawn from tank of molten glassRolled Glass(1920)molten glass poured onto to two rollers to achieve an even thickness,making polishing easier.Used to make patterned and wired glass.Float Glass(1959)molten glass poured onto bed
6、 of molten tin and drawn off in continuous ribbon.Gives high quality flat glass with even thickness and fire polish finish.320 float-glass lines worldwide第5页/共75页6Melting furnaceFloat bathCooling lehrContinuos ribbon of glassCross cuttersLarge plate lift-off devicesSmall plate lift-off devicesRaw ma
7、terial feedTheFloat-GlassProcessOperates non-stop for 10-15 years6000 km/year0.4 mm-25 mm thick,up to 3 m wide第6页/共75页7The Float Glass Process第7页/共75页8Raw materials第8页/共75页9Melting Furnace第9页/共75页10Float Bath第10页/共75页11Float Glass Plant第11页/共75页12The Float-Glass ProcessFine-grainedingredients,closel
8、ycontrolledforquality,aremixedtomakebatch,whichflowsasablanketontomoltenglassat1500Cinthemelter.Thefurnacecontains2000tonnesofmoltenglass.Afterabout50hours,glassfromthemelterflowsgentlyoverarefractoryspoutontothemirror-likesurfaceofmoltentin,startingat1100Candleavingthefloatbathasasolidribbonat600C.
9、Despitethetranquillitywithwhichfloatglassisformed,considerablestressesaredevelopedintheribbonasitcools.第12页/共75页13Raw MaterialsOxide%in glass Raw material sourceSiO272.2SandNa2O13.4Soda Ash(Na2CO3)CaO8.4Limestone(CaCO3)MgO4.0Dolomite(MgCO3.CaCO3)Al2O31.0Impurity in sand,Feldspar or CalumiteFe2O30.11
10、Impurity in sand or Rouge(Fe2O3)SO30.20Sodium sulphateC0.00Anthracite第13页/共75页14Raw materialsSiO2Very durable,BUT high melting point(1700C)!+Na2OMelts at a lower temperature,BUT dissolves in water!+CaOMore durable,BUT will not form in bath without crystallisation+MgOGlass stays as a super-cooled liq
11、uid in bath,no crystallisation+Al2O3Adds durability+Fe2O3Adds required level of green colour for customer第14页/共75页15Chemistry of GlassImportant glassmaking chemistry:basic reactionsNa2CO3 +SiO2 1500C Na2SiO3 +CO2Na2SiO3 +x SiO2 Na2SO4 (Na2O)(SiO2)(x+1)Digestion第15页/共75页16Composition of Glass第16页/共75
12、页17Structure of GlassRandom network of SiO4-tetrahedral units.Na-O enter Si-O network according to valency Network FormersCa and Mg Network Modifiers make structure more complex to prevent crystallisation 第17页/共75页18Body-tinted GlassIonResulting Colour of GlassFerrous(Fe2+)BlueFerric(Fe3+)YellowFe2+
13、Fe3+GreenSelenium(SeO2)BronzeCobalt(Co2+)Grey/BlueNickel(Ni2+)Grey第18页/共75页19CIE L a*b*colour space第19页/共75页20CIE L a*b*colour space第20页/共75页21Functions of a WindowLight in homes,officesLight out shops,museum displaysHeat in heating dominated climatesHeat out cooling dominated climatesCan change pro
14、perties of glass by applying coatings to the surface第21页/共75页22Making a window functional-coatingsA wide variety of coating technologies are utilised by the glass industrySpray PyrolysisPowder SprayChemical Vapour DepositionSputter CoatingThermal Evaporation CoatingsSol Gel CoatingsThese are applied
15、On Line i.e.as the glass is produced on the float lineOff Line i.e.coating not necessarily produced at the same location第22页/共75页23Variations of CVDAtmospheric Pressure APCVDLow Pressure-LPCVDAerosol Assisted-AACVD Metalorganic MOCVDCombustion/Flame CCVDHot Wire/Filament HWCVD/HFCVDPlasma Enhanced-P
16、ECVDLaser Assisted LACVDMicrowave Assisted MWCVDAtomic Layer Deposition ALD第23页/共75页24Chemical Vapour Deposition第24页/共75页25Chemical Vapour DepositionMaingasflowregionGasPhaseReactionsSurfaceDiffusionDesorptionofFilmPrecursorByProductsDiffusiontosurface第25页/共75页26Chemical Vapour DepositionAnimation k
17、indly supplied by Dr.Warren Cross,University of Nottingham第26页/共75页27CVD processes and parametersProcessParametersTransportPrecursorsGasphasereactionPressure,temperature,flowconditions,boundarylayerthickness,gasphaseconcentration,precursors,carriergasDiffusionPressure,temperature,flowconditions,boun
18、darylayerthickness,gasphaseconcentrationAdsorptionTemperature,gasphaseconcentration,numberandnatureofsitesSurfacereactionTemperature,natureofsurfaceDesorptionofby-productsTemperature,pressure,natureofsurfaceDiffusiontolatticesiteTemperature,surfacemobility,numberofvacantsites第27页/共75页28CVD Precursor
19、 PropertiesVolatile gas,liquid,low melting point solid,sublimable solidPureStable under transportReact/Decompose cleanly to give desired coating minimise contaminantsCan be single source or dual/multi-source第28页/共75页29CVD PrecursorsSingle Source pyrolysis(thermal decomposition)Ti(OC2H5)4 TiO2+4C2H4+
20、2H2O(400 C)Oxidation SiH4(g)+O2(g)SiO2(s)+2H2(g)Reduction e.g.WF6(g)+3H2(g)W(s)+6HF(g)Dual source e.g.TiCl4(g)+4EtOH(g)TiO2(s)+4HCl(g)+2EtOEt(g)第29页/共75页30Dual Source and Single Source PrecursorsFilmDual SourceSingle SourceGaAsGaCl3+AsH3Me2Ga(AsH2)TiNTiCl4+NH3Ti(NMe2)4WSiWCl6+SiH4W(SiR)4TiO2TiCl4+H2
21、OTi(OiPr)4CdSeCdMe2+H2SeCd(SeR)2第30页/共75页31Transport of PrecursorsBubblerforliquidsandlowmeltingsolidsDirectLiquidInjectionsyringeandsyringedriverforliquidsandsolutionsSublimationforsolidshotgaspassedoverheatedprecursorAerosolofprecursorsolutions第31页/共75页32Effect of Temperature on Growth RateIndepen
22、dent of temperature第32页/共75页33Flow conditionsLaminar Flow regimeTurbulent Flow Regime第33页/共75页34Reynolds NumberDimensionless number describing flow conditionsr=r=Mass density related to concn and partial pressureu=average velocitym=viscosityL=relevant length,related to reactor dimensionsIf Re 1000 f
23、ully turbulent flowReality is between the two extremes第34页/共75页35Dimensionless NumbersReducesthenumberofparametersthatdescribeasystemMakesiteasiertodeterminerelationshipsexperimentallyForexample:DragForceonaSphereVariables:Force=f(velocity,diameter,viscosity,density)Canbereducedto2“dimensionlessgrou
24、ps”:Dragcoefficient(CD)andReynoldsnumber(Re)第35页/共75页36Dimensionless NumbersLaminar flow regimeTurbulent flow regimeExperimental values of CD for spheres in fluid flows at various Re第36页/共75页37Boundary Layer gas velocityFrictional forces against reactor walls decrease gas velocity The boundary layer
25、 thickness can be estimated from:第37页/共75页38Boundary Layer-temperatureContact with hot surfaces increases temperature第38页/共75页39Boundary Layer precursor concentrationDepletion of precursor decreases gas phase concentration第39页/共75页40Nucleation and GrowthVan der Waals type adsorption of precursor to
26、substratePrecursors then diffuse across surfacePrecursors diffuse across boundary layer to surfaceAnd can be desorbed back into main gas flowOr can find low energy binding sites to coalesce into filmMain Gas Flow第40页/共75页41Nucleation and GrowthSubstrate TemperatureGrowth RateSurface DiffusionCrystal
27、linityLowHighSlowrelativefluxofprecursorsAmorphousnocrystallinestructureHighLowFastrelativetofluxofprecursorsEpitaxialreplicatessubstratestructureIntermediateIntermediateIntermediatePolycrystalline第41页/共75页42Growth Mechanisms(b)Frank-van der MerweLayer growth(c)Stranski-KastanovMixed layered and isl
28、and growth(a)Volmer-WeberIsland growth第42页/共75页43Thin Film AnalysisMany techniques are used to characterise thin filmsExamples includeXRD crystallinity,phaseXRR layer thickness,layer roughnessSEM/EDX/WDX morphology,thickness,compositionRaman phase,bondingFTIR phase,bondingXPS composition,depth profi
29、ling,dopingSIMS composition,depth profiling,dopingAFM roughness,surface morphologyTEM crystalline structure,crystal defectsAnalysis of functional properties第43页/共75页44CVD on GlassFor on-line coating of glass we require:High growth rates required thickness in 100 nm/s possibleLow precursor efficiency
30、 10%SiCxOy(70 nm)SnO2:F(350 nm)GlassSiH4+C2H4+CO2SiCxOy+H2O+otherby-productsUsedascoloursuppressionandbarrierlayer第56页/共75页57Low Emissivity CoatingGenerallybasedonSnO2:F(TransparentConductiveOxide)SiCOunderlayerusedascoloursuppressant第57页/共75页58Low-E and Solar Control Coatings第58页/共75页59Self-Cleanin
31、g GlassTwomechanisms:SuperhydrophilicityPhotocatalyticdegradationoforganicmatter.TiO2coating第59页/共75页60SuperhydrophilicityOxygen vacanciesTiO-TiOTiHTiTiTiH+TiOTiOTiTiOTiOTiHHH2O(OH-,H+)Water dropletsUniform water filmUV illumination timeContact angleooooooodarkUV第60页/共75页61Photocatalytic ActivityUlt
32、rabandgapirradiationofTiO2GenerationofelectronholeinvalencebandHolemigratestothesurfaceandresultsinoxidationoforganicmaterialValenceBandConductanceBandOxidationReductionAA+BB-h+hn第61页/共75页62Semi-conductor PhotocatalysisA.Mills,S Le Hunte,J.Photochem.Photobiol A,1997,108,1-35.第62页/共75页63CVD of ActivT
33、MSiO2(30 nm)TiO2(17 nm)GlassSiH4+O2+C2H4 SiO2+by-productsUsed as barrier layer to prevent diffusion of Na ions into TiO2 layerTiCl4+EtOAc TiO2+HCl+organic by-productsLaminar Flow regimeReasonable growth rates and precursor efficiency第63页/共75页64ActivTM第64页/共75页65ActivTM第65页/共75页66ActivTM第66页/共75页67Su
34、perhydrophilicity15 mins UV Exposure30 mins UV Exposure45 mins UV ExposureBefore UV Exposure第67页/共75页68Photocatalytic Effect UV-AbsorptionO2-OH*Organic SoilHH2 2O+COO+CO2 2GlassBarrier LayerTiO2-Layer第68页/共75页69Photocatalytic EffectThephotoactivityofthecoatingcanbemeasuredbymonitoringthedecompositio
35、nofastandardcontaminantAthinfilmofstearicacid(n-octadecanoicacid,200)isappliedfromamethanolsolutionontothecoatingStearicacidusedasatypicalorganiccontaminantFTIR(Fouriertransforminfra-redspectroscopy)usedtodetectC-HstretchofstearicacidC-HabsorptionintensitymeasuredaftervaryingUVexposure第69页/共75页70Ste
36、aric Acid DecompositionC-HAbsorptionZeroUVexposureC-HAbsorption60minsUVexposure2 340nm第70页/共75页71Pilkington ActivTM第71页/共75页72SummaryScale of the Global Flat Glass IndustryManufacturing Flat Glass Float Glass ProcessCoating Glass Chemical Vapour DepositionExamples of commercial glazing coatings prep
37、ared by CVD第72页/共75页73Recommended ReadingD.W.Sheel and M.E.Pemble Atmospheric Pressure CVD Coatings on Glass,ICCG4 2002 M.L.Hitchman,K.F.Jensen Chemical Vapor Deposition Academic Press,1993W.S.Rees,CVD of Non-metals,VCH,Weinheim,1996 M.Ohring The Materials Science of Thin Films,Academic Press,2001第73页/共75页74First in Glass第74页/共75页75感谢您的观看！第75页/共75页