Fabrication and Thermal Insulating Properties of ATOPVB Nanocomposites for Energy Saving Glass.docx
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Fabrication and Thermal Insulating Properties of ATOPVB Nanocomposites for Energy Saving Glass.docx
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FabricationandThermalInsulatingPropertiesofATOPVBNanocompositesforEnergySavingGlass
FabricationandThermalInsulatingPropertiesofATO/PVBNanocompositesforEnergySavingGlass
ZHANGGangshen1,2,YANWei1,2,JIANGTao1,2*
(1.MinistryofEducationKeyLaboratoryofGreenPreparationandApplicationforFunctionalMaterials,HubeiUniversity,Wuhan,430062,China;2.FacultyofMaterialsScience&Engineering,HubeiUniversity,Wuhan,430062,China)
Abstract:
Pechinimethodwasusedtosynthesizeantimony-dopedtinoxide(ATO)nanoparticles,andthesubsequentsolutionco-blendwasemployedtofabricateATO/PVBnanocomposites.Uv-Vis-NIRspectrashowthattheadditionofATOnanoparticlescansignificantlyenhancethethermalinsulatingefficiencyofATO/PVBnanocomposites.WiththeincreaseofATOcontent,thethermalinsulatingefficiencyisincreased.UvisalmostfullyabsorbedbyallATO/PVBnanocomposites.Vistransmittance-hazespectradisclosethatATO/PVBnanocompositesexhibithigherVistransmittanceofover72.7%andlowerhazeofbelow2%whenATOcontentisintherangeof0.1-0.5wt%.ThethermalinsulatingtestsindicatethatincomparisonwiththepurePVBfilm,nanocompositefilmswith0.1-0.5wt%ATOcanreducetemperatureof1-3℃.Itsuggeststhatthisnovelnanocompositecanbeusedforenergy-savingglass.
Keywords:
Polymer;Nanocomposites;Thermalinsulating;Energy-savingglass
ZHANGGangshen(张刚申):
AssociateProfessor;PhD;E-mail:
970687739@
*Correspondingauthor:
JIANGTao(蒋涛);Professor;PhD;E-mail:
jiangtao@
FundedbyWuhanScienceandTechnologyBureau,HubeiChina(No.200911011428),HubeiScienceandTechnologyDepartment,China(No.2010EGA047)andMinistryofEducationKeyLaboratoryofGreenPreparationandApplicationforFunctionalMaterials,China(No.2010EKLGPAFM018)
1.Introduction
Energysavingandamovetoreducecarbonemissionshavemadeiturgenttodevelopthermalinsulatingglasslikearchitectureglassesandautomobilewindshields.TheautomobilewindshieldsarecommonlymadeofalaminatedglassfilledwithaPVBfilmintermediately.Atpresent,thethermalinsulationofautomobileglassisachievedbypastingfilmonglassesorplatingathinlayerofmetalparticlesonwindshields.However,theseprocessesshowsomeshortcomings,i.e.higherfabricationcostsandblockingelectricalsignalssuchasGPSandmobilephoneetal.Inaddition,theyarenotappropriateforthefabricationofalargeorcurvedglass.
Recently,somematerialswithhighconductivityandlargerefractioncoefficientwithabandgapof0.5~3.1eV,likeTiO2[1],ZnO[2-3],ATO[4-5],indium-tinoxide(ITO)[6],bismuth-dopedtinoxide(BTO)[7],andaluminum-dopedzincoxide(AZO)[8]arereportedtohavehigherthermalinsulatingproperties.Amongthem,ATOnanoparticleshaveastrongscatteringrateinthelow-frequencyinfraredregion[9]andgoodVistransmittance[10],whichmakesATO/PVBnanocompositesexcellentthermalinsulation.ATOnanoparticleshavebeensynthesizedbychemicalcoprecipitation[11],hydrothermalprocess[12],sol-gelmethod[13-16],spraypyrolysis[17-18],andPechinimethod[19].Amongthem,Pechinimethodhasattractedmuchattentionbecauseofitssimpleprocessanduniformproducts[20].However,asfarasweknow,fewstudiesreportthefabricationofATO/PVBnanocomposites.
Herein,theATO/PVBnanocompositeswerepreparedsuccessfullyusingsolutionco-blendprocessbyincorporatingsilanecouplingagentintophysicaldispersionprocess.AndthethermalinsulatingefficiencyandUv-Vis-NIRtransmittanceofATO/PVBfilmsweresystematicallycharacterizedinthiswork.
2.Experimentaldetails
2.1PreparationofATOnanopowders
0.02molCAweredissolvedin100mlEG,andthen0.03molSnCl2·2H2Owasdropped.Afterthat,0.00105molSb2O3wasaddedintothesolutiongradually,andheatedto120℃togetfullymixedsolution.Thegelfromthesolutionagedat50℃for5dayswasheatedat350℃for2handsubsequentlycalcinedat1200℃for1htoformATOnanopowders.
2.2ModifiedanddispersedATOnanopowders
ThecalcinedATOpowderswereaddedinto100mlabsoluteethylalcoholandultrasonicallydispersedfor10min.Thesilanecouplingagent(DB-570,DiamondNewMaterialofChemicalInc.)solutionwasmixedwithATObyamoleratioof1:
1,andthenultrasonicallydispersed.Themixturesweremilledinaballgrinderfor1h,andthendispersedbyultrasonicfor30min.Theco-mixturescanbeobtainedbyremovingtheuppersolutionandthemeasuredsolidcontentisabout27%.
2.3PreparationofATO/PVBnanocomposites
5gPVBpowdersweredissolvedinto100mlabsoluteethylalcoholat75℃.DB-570modifiedATOdispersionliquidwasdropwiseaddedintoPVBsolutionandstirredstronglyfor30min.InordertogetdifferentATO/PVBnanocomposites,theweightratiosofATOnanoparticleswere0.1%,0.3%,0.5%,0.7%,0.9%,respectively.Themixtureweredisperseduniformlyandplacedinovenuntiltherewasnobubbleout,andthenpouredintoPETmouldimmediatelytoobtainATO/PVBnanocompositefilmin50℃oven.
2.4characterizationofATOnanoparticlesandATO/PVBnanocomposites
ThesizedistributionandmicrostructureofATOnanoparticlesweredeterminedbylaserparticlesizedistributioninstrument(ModelHPPS5001)andTEM(ModelTecnaiG20),respectively.ThedistributionandchemicalcompositionofATOnanoparticlesinPVBwereexaminedusingSEM(JOEL-JSM6510LV)andenergydiffractionspectrum(EDS)system,respectively.TheUv-Vis-NIRspectrogramofATO/PVBnanocompositeswasdeterminedbyUv-Vis-NIRspectrophotometer(ModelLambda950).
Thethermalinsulatingeffectofnanocompositefilmwasmeasuredbyathermalinsulatingdevice.Twothermometerswereusedtoreal-timerecordthetemperatureonthesurfaceofATO/PVBfilmandtheinsideofabox.Exceptforthehole,theinsidewallsoftheboxweresealedusing2cmthickfoamstoeliminatethethermalloss.Beforetesting,theroomtemperaturewasmaintainedat17℃byairconditioner.OncethesimulatesunlightirradiatedATO/PVBnanocomposites,theair-conditionerwasswitchedoffimmediately.
A5cm×5cmATO/PVBnanocompositefilmwasplacedbetweentwopiecesofglassestoobtainasandwichglassthroughpreheatingandpreloadingprocessunderhighpressure.VistransmittanceandhazetothissandwichglassweredeterminedbyVistransmittance-hazetester(ModelWGT-S,LabthinkInstrumentsCo.,Ltd.China).
3.Resultsanddiscussion
3.1ThesizeanddistributionofATOnanoparticles
Fig.1ThesizedistributionofATOnanoparticles.
(a)UnmodifiedATO.(b)DB-570modifiedATO.
ItcanbeobservedfromFig.1athatATOnanoparticlesizerangesfrom90to300nmwithanaveragesizeof180nm.Incontrast,asshowninFig.1b,silanecouplingagent(DB-570)modifiedATOnanoparticlesareintherangeof35-50nm.ItrevealsthatDB-570modificationcanpreventtheagglomerationofATOnanoparticles,whichcanbeexplainedbyPosthumus,etal.’stheory[21].Duringthiscourse,silicanecouplingagentishydrolyzedintosiliconalcohol,followedbyadehydrationreactionbetweensiliconalcoholandthehydroxylgroups(-OH)onthesurfaceofATOnanoparticles.–SiO-Mcovalentbondsareformed(MrepresentsthesurfaceofATOnanoparticles).Atthesametime,siliconalcohollinkseachothertoformthinlayerswithreticularstructure,andthesethinlayerscoverthesurfaceofATOnanoparticle.Therefore,DB-570modificationcannotonlyreducetheagglomerationofATOnanoparticlesbutalsofavortheintegrationbetweenATOandPVB.ThesephenomenaarealsoconfirmedbyTEMexamination.AsshowninFig.2a,theagglomerationofATOnanoparticlesisquiteseriousbeforeDB-570surfacetreatment.However,aftermodification,onlyslightaggregationcanbefound(showninFig.2b).
Fig.2TEMimagesofATOnanoparticles.(a)UnmodifiedATO;(b)DB-570modifiedATO
3.2PhotoimageandSEMimagewithinsertEDSpatternofATO/PVBnanocompositefilms
Figure3ashowsthephotoimageofATO/PVBfilmswith0.5wt%ATO.Itisobviousthatthesefilmsdisplaygoodvisualtransparency.ThemicrostructureofATO/PVBnanocompositesisshowninFig.3b.ItcanbefoundthatDB-570modifiedATOnanoparticlesarehomogenouslydistributedintoPVB.TheEDSpatterninsertedinFig.3bshowsthatDB-570modifiedATOnanoparticlesaremainlycomposedofSi,Sn,O,andSb,whichindicatesthatATOparticlesaresuccessfullycladbyDB-570.
Fig.3PicturesofATO/PVBnanocompositefilmswith0.5wt%ATO.
(a)Photoimage.(b)SEMimagewithinsertEDSpattern.
3.3TheUv-Vis-NIRspectrogramofATO/PVBnanocompositefilms
AccordingtothemeasuredUv-Vis-NIRspectrashowninFig.4,100%UvcanbeabsorbedbyallATO/PVBfilms,andover55%Viscanpassthroughwhilemorethan50%NIRisblocked.SincethestandardautomobilewindshieldrequiresaVistransmittancenotlessthan70%[22],itcanbeobservedthatATO/PVBfilmswith0.1-0.5wt%ATOreachtherequirementwithaVistransmittanceof72-85%.And100%Uvisabsorbedwhileover70%NIRiscutoff.ItisevidentthatATOparticlescaneffectivelyscatterNIR.Accordingtothebandtheory,theelectronsofATOnanoparticleswillabsorbUvandmoveuptoexcitedstatefromgroundstatetoformelectronic-holesoncesunlightirradiatesATO/PVBnanocomposites.Whenelectronsmoveback,theotherwavelengthsofphotonswillscatter.ForNIR,nanoparticlesinPVBwillnolongerproduceintrinsicabsorptionbecausephotonenergyislessthantheforbiddenbandwidthofATOnanoparticles.ThefreecarrierssurroundingtheseparticleswillinfluenceNIRphotons.ThedopedSbwillinducetheformationofnumerousfreeelectronic-holes.Inthiscase,alargenumberoffreecarrierssurroundATOnanoparti
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