Expancel®Microspheresapplication guide -Paints and Coatings

Paints...............................................................12ThermalInsulationCoatings..................24ElasticWallandRoofCoatings.............28WaterbornePrintingInks........................36

Introduction to Expancel® Microspheres

Expancel®microspheresaresmallsphericalplasticparticles.Themicrospheresconsistofapolymershell

encapsulatingagas.Whenheated,theinternalpressurefromthegasincreasesandthethermoplasticshellsoftens,

resultinginadramaticincreaseofthevolumeofthemicrospheres.Thegasremainsinsidethesphere.

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ExpansionofExpancelmicrospheres.Thisresultsinadramaticdecreaseofthedensity.Typicalvaluesarefrom1000downto30kg/m3(8.35to0.25lbs/gal).

Thermomechanical propertiesExpancelisavailablewithexpansiontemperaturesintherangeof80-190

oC(175-375

oF).

Expancelcannormallybestoredforalongtimeatroomtemperaturewithoutnegativeeffectsontheproperties;veryhightemperaturesshouldbeavoided.

ElasticityExpancelmicrospheresregaintheiroriginalvolumewhenthepressureisreleased.Expancelcanwithstandseveralcyclesofloading/unloadingwithoutbreaking.

Thisisveryimportantwhenthemicrospheresareusedinshockabsorbentmaterialsbutalsowhenpumpingthemicrospheres;aloneorinvariousmixtures.

Properties ofExpancel® Microspheres

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ExpansioncurvesforsomeExpancelgrades.

Before0barg

During6barg

After0barg

IllustrationofwhathappenswhenExpancelDEisfirstputunderpressureandlaterreturnedtoambientpressure.

ExpansionTheexpansioncharacteristicsaremeasuredusingThermoMechanicalAnalysis(TMA).Thesampleisheatedataconstantrate(inouranalysis20

oC/min,36

oF/min)andthevolumeofthesample

ismeasured.Agraphrepresentingtheexpansioncharacteristicsofthesampleisrecorded(figure1).Fromthisgraph,thevaluesarecalculated.TypicalTMA-graphsofafewgradesareshowninfigure2.

ItisimportanttorememberthatifTmaxis140oC

(284oF)thisdoesnotnecessarilymeanthatthe

processtemperatureshouldbe140oC.

Theexpansionprocessisadelicatebalance.Therelationshipbetweenthesofteningofthe

shell,gastightnessoftheshellandpressureincreasefromthegasinsidethemicrosphereareimportant.Thebalanceisaffectedbyanumberoffactorssuchas:•Polymercompositionoftheshell•Typeofgasinsidethemicrospheres•Chemicalsincontactwiththeshell•Outerpressure•Freeexpansionorinamatrix•Typeofmatrix•Heatingrate

Thepolymercompositionoftheshellisimportantasitdeterminestheglasstransitiontemperatureandthegaspermeabilityoftheshell.Thegasinsidethemicrospheresdeterminesthepressureinsidetheshellatagiventemperature.

ContactwithchemicalscandecreasetheglasstransitiontemperaturesandtherebylowerT-startofthemicrospheres.Chemicalsmightalsoinfluencethebarrierpropertiesandincreasethegaspermeabilityleadingtothesmallerdensityreduction.

Insidethematrixthegaspermeabilitycanbeimprovedduetoitsbarrierproperties.IfthemicrospheresareunderpressurefromtheoutsidethedecreaseinpressurebetweentheinsideandtheoutsideoftheshellcanresultinahigherT-startandsmallerdensityreduction.

Across-linkingmatrix,egrubberorthermoset,canalsopreventsomeofthepossiblemaximumpressureexpansionofthespheres.

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ThegraphfromatypicalTMAanalysis.

TypicalgraphsofsomeExpancelgrades.

Thermal StabilityThethermalstabilityofdifferentgradesofpre-expandedmicrospheresshowsacleardifference.ThedifferentthermomechanicalbehaviourofvariousExpancelgradesmakesitpossibletochooseanoptimalgradeforeachprocessandapplication.

Rankingofthermalstability.

Particle SizeExpancelmicrospheresareavailableindifferentsizesbetween20and120micronsafterexpansion.

ThesizeofExpancelismeasuredbylaserdiffraction,LowAngleLaserLightScattering(LALLS).Themicrospheresinanygivensamplearenotallthesamesize.Thereisaparticlesizedistribution.

Allspheresinthissamplehaveapproximatelythesamerelationbetweendiameterandshellthickness.Thismeansthatthelargemicrospherehasgreatershellthickness-andhencealowergaspermeability-andthereforeitwillexpandslightlybetterthanasmallermicrosphereinthe

samesample.Thismeansthattheparticlesizedistributionthatisrathernarrowforunexpandedmicrosphereswillincreaseafterexpansion.

Thedensityofthemicrosphereshasaninfluenceontheparticlesize.Forinstance,size40microspheresatdensity30kg/m3(0.25lbs/gallon)hasaboutthesamesizeassize80microspheresatadensityof>100kg/m3(0.83lbs/gallon).

Chemical ResistanceExpancelcanbeusedincontactwithmanychemicals,includingsolvents,withoutdiscolorationornegativeeffectsonexpansionorotherproperties.

High PressureExpancelDUhasagoodresistancetohighpressure.TheabilityofExpancelDEtowithstandhighpressurevariesconsiderablywithdensityandparticlesize.Largermicrospheresandmicrosphereswithhigherdensityleadtobetterhighpressureresistance.

Closed CellsExpancelmicrospheresareclosedcells,whichisanimportantpropertyinmanyapplications.

Inawaterbornecoating,suchaspaint,thismeansthatthemicrosphereshavealowwaterabsorptionbutthecoatingwillhaveahighwaterpermeability.Thisiscausedbytheinterfacebetweenthemicrospheresandthesurroundingmatrix.

ExpancelGrade ParticleSize

820 Low 20 Low642 40551 80461 100920 120009 140 High930 High

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Inthisinterface,themoisturetransportisquickcomparedwiththemoisturetransportinthefilmitself.Thisallowsmoistureinthesubstratetoevaporate.

Gas TightnessThepolymershellofExpancelmicrosphereshasbeencarefullydesignedtohavelowgaspermeability.Thisisimportantinmanyapplicationssinceitkeepsthemicrospheresfromleakinggasintothematrix.

Gasleakageintothematrixcanproducepinholesinthematrixandanincreaseddensity.Thedegreeofgastightnessvarieswiththegrade.

Mechanical StrengthExpancelmicrospheresareabletowithstandmanycyclesofloading/unloadingwithoutbreaking.Howeverasthedensityofthemicrospheresdecreasesthisabilitywilldecreaseaswell.

Somechemicalsmayalsoaffecttheelasticityandmechanicalstrength.

Surface ModificationExpancelmicrospherescanbeusedtoachieveanicevelvet-likesurfacebyaddingasmallamounttoacoating.Thiscanbedoneonmetal,paper,fabrics,etc.

InsulationGas-filledclosedcellsarebeneficialinbothelectricalandthermalinsulationapplications.

Expancelmicrospheresareusedincablefillingcompounds.InPetrolatum,therelativepermittivitywasreducedfrom2.2to1.6byadding4%ofExpancelDE.

Thedensitywasreducedfrom900to450kg/m3(7.5to3.8lbs/gallon).

Thethermalconductivityofthermoplasticshasbeenreducedfrom0.2to0.06W/m*K(1.4to0.4Btu*ft/h*ft2*

oF).Thedensitywas

approximately300kg/m3(2.5lbs/gallon).

Thermalconductivitiesof0.07W/m*K(0.5Btu*ft/(h*ft2*

oF)arereportedon

1to1.5mm(0.4to0.6in)thickcoatings.

Internal PressureExpancelmicrospherescanbeaddedtoproduceaninternalpressureinthefinishedproduct.Thisisusedinmanyapplications,forexampleprintingblanketsandpipeinsulationforoffshoreapplications.

Expancelmicrospheresarealsousedtoimprovetheprocess.Theycan,forexample,bemixedwithafillerbeforeaddingabinder.Herethemicrospherescreateapressureinthemoldand,togetherwiththebinder,fillallthevoidsbetweenthefillerparticles.

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Anotherexampleisinjectionmoldingwherethepressureisusedtocounteracttheshrinkingthatoccurswhentheproductiscooled.

DispersabilityExpancelWUiseasytodisperseuniformlyinanaqueousdispersion,butcaremustbetakentochoosethecorrecttypeofdispersingequipment.Therearegradesthatareeasiertodisperseandthereareothersthataremoredifficult.

Thegradesthataremoredifficulttodispersemayrequirearotor/statormixerlikeaSilverstonmixer,whilethegradesthataremoreeasilydispersedmayonlyrequireasimplepropellerstirrerforproperdispersion.

ExpancelDUcanbeeasilydispersedusinggeneraldispersingequipment.

ExpancelWEisfairlyeasytodisperseinanaqueousdispersionusingproperequipment.

ExpancelDEisveryeasytodisperseusinggeneraldispersingequipment.Caremustbetakentoavoiddustingbecauseoftheextremelylowdensity.

Application TechniquesTherearemanydifferentprocessesinwhichExpancelmicrospherescanbeused:

Impregnation-acommontechniqueforprocessingnon-wovens

Lamination-Expancelinacorematerialwillcreatealightweightmaterialwithresilientproperties

Coating-Expancelinacoatinglayerwilladdthicknessandimprovesurfacecharacteristics

Spraying-Sprayingispossible

Molding-ExpancelDEcanbemixedwithmanythermosetmaterialstoformamouldedproductwithlowdensity

Mattingandanti-slip-Expancelcanbemixedinacoatingtomodifysurfacepropertieslikeglossandanti-slip

Injectionmolding-ExpancelDUorMBcanbeusedininjectionmolding

Extrusion-ExpancelDUorMBcanbeusedinextrusionofprofiles,cablesandhoses

ExpancelGrade ParticleSize

642WUDifficult 20 Difficult551WU 40461WU 80007WUFEasy 100054WUFEasy 120920WUFEasy 140 Easy

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DesignationEveryproducthasitsownuniquenamedependingonthecompositionoftheshell,theparticlesize,thedeliveryformand,ifthemicrospheresareexpanded,thedensityofthemicrospheres.

Thefirstthreetofourcharacters,thegrade,areacodeforthepolymertypeandtypeofhydrocarbon,egFG=foodgrade.

Thetwotofourlettersindicatethedeliveryform,egW=wet;D=dry;U=unexpanded;E=expanded;MB=masterbatch.

Thetwotothreedigitsaftertheletterindicatetheapproximateparticlesizeinmicronsafterexpansion.

Thefinald30indicatesthatthetruedensityofthedryproductis30kg/m3(0.25lbs/gallon).IftheproductisWE,thedensityvaluereferstothedensityasadryproduct.

Delivery FormsExpancelmicrospherescanbedeliveredinawidevarietyofdifferentforms.

Unexpandedproductsareusedwhentheprocessinggeneratesenoughheatforthespherestoexpandandthematrixallowsanexpansion.

Pre-expandedproductsareusedinprocesseswhereno,ornotsufficient,heatisgeneratedduringproductionorwhen,forexample,thematrixiscrosslinkingattemperatureslowerthantheexpansiontemperatureofthemicrospheres.

Wetmicrospheres(WU,WUF,WE)arechosenforprocessesthatcontainwaterwhilethedryversions(DU,MB,DE/DET)arechosenwhennowatercanbepresent.

Theunexpandedmicrospheresactasfoamingagentswhilethepre-expandedmicrospherescanbeseenaslightweightfillers.

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SolidContent DensityofExpancelVariety Description % kg/m3 lbs/gallon

WU Wet,unexpanded 60to80 1000to1300 8.3to10.8WUF Wet,unexpanded 60to80 1000to1300 8.3to10.8DU Dry,unexpanded >99 ~1000 ~8.3DUT Dry,treated,unexpanded >99 ~1000 ~8.3MB Dry,unexpandedmixedwithamatrix 62to65 1000 8.3WE Wet,expanded 15 ~30 0.25DE Dry,expanded >99 25to70 0.21to0.58DET Dry,treatedexpanded >99 25 0.21

DeliveryformsofExpancel

StorageExpancelmicrospheresareverystablewhenstoredinaplacewithnormaltemperatures.

ExpancelWU(F)mustbestoredinacool,well-ventilatedareainawaythatkeepsthemicrospheresfromdrying.

Ifmicrospheresbegintodrybecausethebaginthedrumisopenorpunctured,thedispersabilitywilldroprapidlycausingproblemssuchaswhitespotsorunevennessinthefinishedproduct.

Becauseofthis,itisveryimportanttocloseabagwhenitisopenedandonlysomeofthecontentused.

ExpancelDU(T)canbedamagedbyexcessiveheatduringstorage.Thisheatcancauseleakageoftheencapsulatedhydrocarbonresultinginpoorexpansion.

ExpancelMBmustbestoredinacool,well-ventilatedareaawayfromdirectsunlight.

ExpancelWEmustbestoredinacool,well-ventilatedareainawaythatkeepsthemicrospheresfromdrying.Poordispersabilitywillresultfromallowingdryingtotakeplace.

Separationcanalsotakeplaceasaresultofthelargedensitydifferencebetweenthemicrospheresandthesurroundingwater.Thisisbestpreventedbystoringthebagslyingdownflat.

ExpancelDE(T)mustbestoredinadry,cool,well-ventilatedareatocontrolairborneparticles.

Form pH Grade RecommendedUseUnexpandedWU(F) Acidic 820 DU(T),MB Acidic 642 Acidic 551 Acidic 461 Lowtemperatureapplications Acidic 051 Alkaline 920 Mediumorhightemperatureapplications Neutral 031 Neutral 007 VerygoodexpansioncapacityExpandedWE,DE(T) Acidic 461 Mediumsolventresistance Alkaline 920 Excellentsolventresistance

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Recommendations

Expancel® Microspheresrecommended grades

Polyester Putties461DET40d25920DET40d25461DE20d70(alternativegrade)

461DE20d60(alternativegrade)

Thermoset Materials461DET40d25920DET40d25(alternativegrade)

551DU40(alternativegrade)

Printing Inks Water007WUF40

Tech Textiles & Non-Woven551WU40007WUF40

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Paint461WE40d36461WE20d36(alternativegrade)

921WE40d24(alternativegrade)

461DE20d70(alternativegrade)

Cable Gel461DET40d25920DET40d25(alternativegrade)

Vinyl Foam909DU80051DU40(alternativegrade)

920DU40(alternativegrade)

Crack Filler461WE40d36

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Cultured Marble461DET40d25551DE40d42(alternativegrade)

Model Making Board461DET40d25551DE40d42(alternativegrade)

920DET40d25(alternativegrade)

Caulks and Sealants461DET40d25920DET40d25(alternativegrade)

UBC and Sealants909DU80930DU120

Thermoplastics930MB120951MB120930DU120(alternativegrade)

951DU120(alternativegrade)

Lightweight Foam551DU40551DE40d42930DU120(alternativegrade)

951DU120(alternativegrade)

Silicon Rubber053DU40909DU80920DET40d25(alternativegrade)

Shoe Soles093DU120930DU120951DU120950DU80(alternativegrade)

930MB120(alternativegrade)

Leather Finishing461WE20d36461WE40d36461DET40d25(alternativegrade)

Artificial Leather909DU80920DU40093DU120051DU40(alternativegrade)

Wall and Roof Coating461WE40d36461DET40d25(alternativegrade)

Modelling Clay461DET40d25461WE40d36(alternativegrade)

Thermal Insulation Coating461WE40d36921WE40d24(alternativegrade)

Concrete461WE40d36921WE40d24(alternativegrade)

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Expancel® Microspheresin Paint

Expancelgivesadvantagestopaint:n reduceddensityn betterapplicabilityn higherwater

vaporpermeabilityn lowerwaterabsorptionn betterfillingcapacityn lowermaterialcostn shorterdryingtimen improvedmattingeffect

n lowemissionofVOC

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Waterborne PaintsAsanadditivetowaterbornepaintsanExpancelWEgradeisrecommended.Theseareexpandedtoaverylowdensity,thetruedensitybeing36kg/m3(0.30lbs/gal).Theyareavailableinthreesizes,withameanparticlediameterofapproximately80,40and20µmrespectively.Thelowdensitymicrospheresaremoist,whichmakeshandlingeasier.921WE40d24isachlorine-freealternative.

Expancelgradesusedinthepaintindustry:

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Grade 461WE40d36 461WE20d36 921WE40d24ed

Particlesizeweightaverageµm 30-50 20-30 35-55

Truedensity(inair) 36+3 36+3 24+3 kg/m3(lbs/gal) (0.3+0.025) (0.3+0.025) (0.2+0.025)

Solidcontent% 15+2 15+2 15+1.5

Reduced WeightByusing0.5%Expancel,theweightofa12litre(3.17gal)paintpotwillbereducedfromabout18kg(39.7lbs)to14kg(30.9lbs).

Thedensityofthepaintdecreasesto1.20kg/cm3(10lbs/gal)and,thus,thevolumeperkgpaintincreasesby30%.

ApplicationThepaintcaneasilybeappliedbyrollerorbrushbecauseofthesphericalformoftheparticles.Sprayinginairlessspraygunsisalsopossible.AlightweightpaintcontainingExpancel,withequalviscosityasaconventionalpaint,doesnotsplashtothesameextentwhenusingaroller.Theexpandedmicrospheresarehighlyelasticandwithstandhardmechanicaltreatmentwithoutdamage.

Intexturedcoatings,Expancelmakesiteasiertogetthestructuralfillermoreevenlydistributed.

ThedryingtimeofapaintwithExpancelwillbeshorterduetoahighersolidcontentbyvolume.

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Water Vapor PermeabilityPaintswithExpancelWEaremorepermeablethancorrespondingstandardpaints.ExpancelWEcanbeusedasanadditivetoregulatethewatervaporpermeabilityinlightexteriorpaintfilmsandprimercoatings.

Water AbsorptionPaintswithExpancelWEaremorehydrophobicthancorrespondingstandardpaints.Oneofthereasonsforthedegradationanddestructionofapaintfilmisthewaterabsorption.TheadditionofExpancelWEwilldecreasethewaterabsorptioncausingadelayinthedestructionandreducetherateofdestructioninpaint.

Properties of Paints with Expancel®

Hiding Power - OpacityOneoftheobjectiveswhenmakingalightweightformulationwithExpancelistoreplacepartoftheheavyfillerswithExpancelmicrospheres.Itisthenimportanttoachieveaveryhighpackingdegreeinordertoimprovethehidingpower.Unfilledspacesbetweentheparticlesarenottoberecommendedinthiscaseasthemicrospheresthemselvescontributewithalotofunfilledspacesinthefilm.

Surface FinishExpancelmicrospherescanbeusedasamattingagentinpaintswithlowgloss.Themicrospheresprovideamattfinestructuredfinishtothesurface.

Filling CapacityApaintwithExpancelhasabetterfillingcapacity,whichmeansahighercapacitytocovercracksinthesubstrate.Thisisachievedbytheincreasedsolidcontentbyvolume.Anotheradvantageisshorterdryingtime.

ViscosityAsuitablelevelofviscosityofalightweightpaintwithExpancelcaneasilybeobtainedbyusingmoreorlessthickener.Adecreaseinviscositybyaddingwaterisnotrecommendedsincetheopacitywillbenegativelyaffected.

IfExpancelmicrospheresareaddedto

aconventionalformulation,ortoaformulationnotintendedtocontainanylightweightfiller,theviscositywillincreaseconsiderably.

Material CostExpancel

hasalowbinderdemandbecause

theoilabsorptiononavolumebasisisverylow.ThismakesitpossibletoincreasethePigmentVolumeConcentrationwithoutsacrificingquality.TherawmaterialcostsperlitrepaintwillbelowerwithExpancel

microspheres.

Astandardformulationofaninteriorflatwallpaintwillshowacostsavingof3-5%perlitrebyusingExpancel,whileanexteriorpaintwillshowacostsavingofapproximately7%.

Storage StabilityThestoragestabilityofthepaintwillnotbeaffectedwhenusingExpancel

microspheres

asalightweightfiller.ThereisnoriskofExpancel

microspheresflotatingataviscositysuitableforpainting.pHshouldbekeptbelow8.3inordertoavoiddiscolouration.

Health AspectsExpancel

microspheres

inlightweightpaintswill

notgivetheusersanyhealthorsafetyproblems.

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TwothingsareofutmostimportanceconcerningthepreparationofExpancel.TheadditionofExpancel

oughttotakeplacejustafterdispersing

theheavyfillersandtheperiphericalspeedshouldbehighenoughtodisperseExpancelWEmicrospherescompletely.

ThefollowingdispersionprogrammeissuitabletoobtaincompletelydispersedparticlesatthemanufacturingofalightweightpaintwithExpancelWE.

WaterDispersingagentsPreservativeDefoamerWettingagentPigmentOpacifyingextenderFillers

Themixtureisdispersedfor10minutesataperiphericalspeedofatleast10m/s(32.8ft/s).

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Expancel WE

ThickenerpH-bufferCoalescent

Dispersefor5minutesataperiphericalspeedofatleast10m/s(32.8ft/s).

Binder

Dispersefor5minutesatalowerperiphericalspeedeg5m/s(16.4ft/s).

DefoamerWater

Thecomponentsaremixedtogetherbymeansofahighspeeddissolver.Theingredientsareaddedintheordersuggested.Itisveryimportanttoachieveamixturewithnoagglomerates.

Preparation ofLightweight Paints with Expancel WE

Therefore,dispersionshouldtakeplaceinthreestepsduringpreparation:

1. fortenminutesafteradditionofthemineralfiller.

2. forfiveminutesafteradditionofthethickeners tothemixtures(ifcellulosethickenerin powderformisuseditmustbedissolved andthemixturethickenedbeforethedispersion ofExpancelWE).

3. forfiveminutesafteradditionofthebinder.

Theperiphericalspeedofthedissolvingdiscshouldbeatleast10m/s(32.8ft/s).Alowerspeedcanresultinincompletedispersionofthemicrospheres.Theair,whichisoftenwhippedintothepaintduringpreparation,isremovedbyaspecialdeaerationdiscinlaboratoryscale.

Ifnecessary,asmalleramountofasuitableanti-foamingagentcanbehelpful.Inthisphasethedissolvermayworkatalowspeedtogivetheairbubblesagoodchancetoescape.

PleasenotethatdispersionanddeaerationmightbemoreimportantforpaintswithExpancelWEthanforpaintswithoutmicrospheres.

Expancel461WE20d36isrecommendedduetoitsgooddispersability.

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Dispersability of Expancel DE

ThedryExpancelDEgradescanbesprayedwithwatertomakethehandlingeasier.TheDEgradesobtainaproperdispersionatloweragitationcomparedtotheWEgrades.

Thewettingprocedureisperformedrapidly.Themicrospherescanbewetteddirectlyinthebag.

TheviscositywasmeasuredwithaBrookfieldRVTViscosimeterspindle6.Therheologyoftheguidingformulationshowsapseudoplasticflow.

Theviscositywasdeterminedafterthreedaysofstorage.

Inordertokeeptheconsumptionofbinderonalowlevelinalightweightpaintitisofgreatimportancetocalculatetherightpackingdegreeoftheusedfillers.Insuchcases,partsoftheheavyfillerscaneasilybereplacedbymicrosphereswithoutadditionalbinder.

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Whenkeptinmetalcontainersitisnecessarytoaddanantirustagenttotheformulation,usuallysodiumnitriteandsodiumbenzoate.

Topreventthegrowthoffungiinplaceswithhighhumidityafungicidemaybeaddedtotheformulation.

Theguidingformulationsarebasedonlaboratorytestsonly.Aprospectiveusershoulddeterminethesuitabilityoftheformulationsbeforeadoptingthemonalargescale.

Comments to the Guiding Formulations

Formulation no 1Interiorflatpaintcontaining2%(0.3%dry)Expancel461WE40d36vscorrespondingstandardpaint.

Standard Modifiedwith2% Paint Expancel461WE40d36Water 400.0 409.0Sodiumtripolyphosphate,10% 6.0 6.0PigmentdisperserA,10% 6.0 6.0ProxelGXL 2.0 2.0TritonCF-10,10% 20.0 20.0Foamaster8034 2.0 2.0TyloseMHB30000YP 3.0 3.0TitaniumdioxideR-FD-1 120.0 120.0SocalP2 60.0 90.0MicrodolSuper 120.0 140.0OmyaBLP-2 118.0 50.0Expancel461WE40d36,15% -- 20.0Acrylicbinderemulsion,60% 100.0 100.0Texanol 10.0 10.0Foamaster0 2.0 2.0Water 16.5 11.5AMP95 2.5 1.0AcrysolTT-935,30% 12.0 8.5Total 1000.0 1000.0

Constants and properties

SpecificGravity g/cc(lbs/gal) 1.40(11.7) 1.22(10.2)SolidContent,weight % 49.8 47.8SolidContent,volume % 26.9 34.7ViscosityBrookfield#6,50rpm mPas 7900 5400PVC % 72.0 80.9HidingPower-Contrastratiogapclearance 180µm 98.8 97.5Filmthickness 75µmdry 97.8 97.5Brightness457mm 89.5 90.5Gloss60

o 2 2

pH 8.6 8.3Costsaving(approx) % -- 4.3

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Formulation no 2 - 3 - 4InteriorflatpaintcontainingExpancel461WE20d36vscorrespondingstandardpaint.

Standard Modifiedwith Paint Expancel461WE20d36 2% 3% 4%Water 245.0 255.0 255.0 275.0Sodiumtripolyphosphate,10% 6.0 6.0 6.0 6.0PigmentdisperserA,10% 6.0 6.0 6.0 6.0TritonCF-10,10% 10.0 10.0 10.0 10.0ProxelGXL 1.0 1.0 1.0 1.0Foamaster8034 2.0 2.0 2.0 2.0Tiona388 60.0 60.0 60.0 60.0SocalP2 100.0 130.0 145.0 160.0OmyaVioletD 170.0 140.0 140.0 140.0Calciumcarbonate5µm 160.0 105.0 75.0 50.0TalcumM15 50.0 50.0 50.0 50.0Expancel461WE20d36,15% -- 20.0 30.0 40.0CellosizeQP-30000H,3% 30.0 60.0 50.0 40.0CollacralPU85,30% 10.0 10.0 10.0 10.0RopaqueUltraE,37.5% 30.0 30.0 30.0 30.0Texanol 6.0 6.0 6.0 6.0Acronol290D,50% 100.0 100.0 100.0 100.0Foamaster0 2.0 2.0 2.0 2.0Water 12.0 7.0 22.0 12.0Total 1000.0 1000.0 1000.01000.0

Constants and properties

SpecificGravity g/cc(lbs/gal) 1.40(12.9)1.29(10.8)1.19(9.9) 1.12(9.3)SolidContent,weight % 61.2 56.1 55.3 54.7ViscosityBrookfield#6,50rpm mPas 6000 5700 54005300PVC % 81.0 86.0 88.0 89.0HidingPower(contrastratiogapclearance)180µm 99.4 99.0 99.0 98.6Spreadingrate(contrastratio98%) m2/l 10.3 9.5 9.6 9.8WetFilmthickness(contrastratio98%) µm 97.0 105.0 104.0 102.0Brightness457mm 86.2 86.8 86.8 86.9Gloss60

o 2 2 2 2

ScrubresistanceDIN53778 ca2000 ca2000 ca2000ca2000Costsaving(approx) % -- 4.6 5.1 5.7

Formulation no 5Exteriorhousepaintcontaining2%(0.3%dry)Expancel461WE20d36vscorrespondingstandardpaint.

Standard Modifiedwith2% Paint Expancel461WE20d36Water 186.2 166.5Natrosol250HR 3.8 3.5Oratan731,10% 20.0 20.0TritonCF-10,10% 20.0 20.0Sodiumtripolyphosphate10% 10.0 10.0Nopco8034 2.0 2.0Ethyleneglycol 10.0 10.0TitaniumdioxideRK-B2 200.0 200.0MicrotalcITExtra 70.0 100.0Syenex10NephelineSyenite 110.0 80.0Expancel461WE20d3615% -- 20.0Acrylicbinderemulsion,60% 330.0 330.0Propyleneglycol 10.0 10.0ProxelGXL 3.0 3.0Texanol 10.0 10.0NopcoNXZ 2.0 2.0Water 13.0 13.0Total 1000.0 1000.0

Constants and properties

SpecificGravity g/cc(lbs/gal) 1.39(11.6) 1.23(10.3)SolidContent,weight % 60.8 61.5SolidContent,volume % 41.0 49.0PVC % 39.0 56.0ViscosityBrookfield#6,50rpm mPas 4900 5000StorageStability 14daysat50

oC Pass Pass

HidingPower-Contrastratiogapclearance 180µm 98.7 98.3Filmthickness 75µmdry 98.2 97.7Brightness457mm 89.1 89.1Gloss60

o 5 2

pH 8.3 8.1Costsaving(approx) % -- 6.8

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Formulation no 6Texturecoatingcontaining3%(0.45%dry)Expancel461WE20d36vscorrespondingstandardpaint.

Standard Modifiedwith3% Paint Expancel461WE20d36Water 150.4 152.4ProxelGXL 2.0 2.0Potassiumtripolyphosphate10% 0.8 0.8Oratan731,25% 6.0 6.0FoamasterNXZ 0.8 0.8Titaniumdioxide 50.0 50.0Syenex20NephelineSyenite 100.0 70.0Calciumcarbonate,2µm 200.0 210.0CellosizeQP-15000H 6.0 6.0Acrylicbinderemulsion,60% 200.0 200.0Expancel461WE20d3615% -- 30.0BentoneEW,10% 4.0 2.0Texanol 10.0 10.0Ethyleneglycol 10.0 10.0StructurefillerQuartz-sand0.02-0.5mm 90.0 70.0StructurefillerQuartz-sand0.02-0.5mm 170.0 180.0Total 1000.0 1000.0

Constants and properties

SpecificGravity g/cc(lbs/gal) 1.70(14.2) 1.33(11.1)SolidContent,weight % 74.2 71.5SolidContent,volume % 54.0 60.0PVC % 70.0 79.0Costsaving(approx) % -- 7.8

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Expancel® Microspheresin Thermal Insulation Coatings

AddingExpanceltoaninsulationcoatingreducesconductivity,whichcanhelp

toreducepowerconsumption.

11

ExpandedthermoplasticExpancelmicrosphereswithlowdensityareoftenusedasalightweightfiller.TherearealsoanumberofvaluablepropertiesthataretechnicallyimprovedwhenExpancelmicrospheresareincorporated.

Whenexpandedmicrospheresareaddedtoanacryliccoating,anessentialincreaseinthermalinsulationisachieved.Thisiscausedbygas-filledvoidsinthecoatingthatarecreatedbytheexpandedmicrospheres.

Thethermalinsulationcoatingisbasedonahighlyelasticaqueouspolymeremulsion.ThevolumeextentofexpandedExpancelmicrospherescouldbeadjusteddependingontherequiredinsulationcapacityofthecoating.

What Grade is Best?

Asthecoatingiscuredwithoutadditionalheat,wetpre-expandedExpancelmicrospheresarerecommendtobuildupafoamedstructureinthecoating;egExpancel461WE40d36orExpancel921WE40d24.Drypre-expandedgradesarealsoavailable.

Preparation

Thethermalinsulationcoatingcanbemixedandpreparedwithrotationaldeviceslikedissolver,butterflymixerorplanetarymixer.Expancelmicrospheresareeasilydispersedandcanbeaddedtothemixtureasthelastcomponent.

25

Application

Exteriorroofsandwallsofhouses,buildings,industrialfacilitiesandwarehousescanbeprotectedbythermalinsulationcoatings.Itcanbeusedonsurfaceslikeconcrete,woodandmetalsheets.

Itisrecommendedtoapplyalayerwithadrythicknessof1.0to1.5mmtoachieveasufficientinsulation.Theinsulationcoatingiseasytoapplywitharoller,brushorbyspraying.

High PVC-value

Expancelcontributeswithalargevolumetothecoating.ThebinderdemandofExpancelislowerbyvolumecomparedtoconventionalmineralfillers.Thespecificsurfaceoftheroundparticlesissmall.

Thermal Conductivity and Thermal Insulation

ThethermalconductivityandinsulationareinfluencedbytheadditionofExpancelandthecontentofmineralfiller.

AmineralfillerlikeCaCO3willincreasethethermalconductivity.Expancel,withtheporousstructureinthecoating,willreducethethermalconductivityandimprovethermalinsulation.

10

Further Properties

Theexpandedmicrospheresareclosedcells.Thiswillimprovethewaterresistanceofacoating.

PaintswithExpancelhaveahigherwatervapourpermeabilitythancorrespondingstandardpaints.

26

TheUVcrosslinkingtechnologyoftheacrylicbinderhasbeenoptimisedtoguaranteealowdirtpick-upperformance.Duetothehighvolumesolidsofacoatingwithexpandedmicrospheres,thedryingtimeisshortened.

ThehighvolumecontributionfromthemicrosphereswillgivealowdensityandalowVOC-emission(g/l)oftheinsulationcoating.

Guiding formulation

BaseCoating Weight Volume g % cc %Grind Water 70.0 9.3 70.0 11.5 Orotan731A 10.7 1.4 9.7 1.6 TritonDF-16 2.2 0.3 2.1 0.3 FoamasterNXZ 3.0 0.4 3.3 0.6 Propyleneglycol 18.0 2.4 17.4 2.9 TioxideTR92 80.0 10.7 20.0 3.3 Durcal5 100.0 13.3 36.4 5.9Premix FoamasterNXZ 3.5 0.5 3.9 0.7 Water 13.0 1.7 13.0 2.1Let down Elastene404 419.0 55.9 402.9 66.2 AcrysolRM-8W 20.0 2.7 19.2 3.2Premix Water 4.6 0.6 4.6 0.8 DMAEDimetylaminoethanol 0.7 0.1 0.8 0.1 AcrysolASE-60 5.3 0.7 5.0 0.8

Totals 750.0 100.0 608.3 100.0

1127

AdditionofExpancel921WE40d24 Weight Volume g % cc % BaseCoating 307.5 89.4 249.4 57.4 Expancel921WE40d24 36.5 10.6 184.9 42.6 Drymicrospheres 3.7 1.1 152.1 35.0 Waterfrommicrospheres 32.9 9.5 32.9 7.6 Totals 344.0 100.0 434.3 100.0

Properties % Pigmentvolumeconcentration % 63.7 Volumesolids % 67.7 Weightsolids % 60.0 Density g/cm3

0.80 Viscosity(Brookfield,spindle5/6rpm) mPas 55000-60000 Viscosity(Brookfield,spindle5/3rpm) mPas 65000-70000

AdditionofExpancel920DET40d25 Weight Volume g % cc % BaseCoating 307.5 89.3 249.4 57.4 Expancel920DET40d25 3.8 1.1 152.0 35.0 FreeWater 33.0 9.6 33.0 7.6 Totals 344.2 100.0 434.4 100.0

Properties % Pigmentvolumeconcentration % 63.7 Volumesolids % 67.8 Weightsolids % 60.1 Density g/cm3

0.80 Viscosity(Brookfield,spindle5/6rpm) mPas 50000-55000 Viscosity(Brookfield,spindle5/3rpm) mPas 60000-65000

10

Expancel® Microspheresin Elastic Wall

and Roof Coatings

11

Elasticwallandroofcoatingisahighlyflexibleexteriorcoatingusedoncement,concreteandsimilarmaterials.Itwithstandswater,whichcouldotherwisecausecrackingandfreeze-thawdegradationinthesubstrate.

Thiscoatingshouldalsobeaneffectivebarrierforcarbondioxideandotheracidgasesintheatmospherethatmightotherwiseneutralisethealkalinityofthesubstrate.

Atthesametimethecoatingshouldbepermeableenoughtoequalisethedifferencesinpartialpressureofwatervaporthatappearbetweenthesubstrateandtheexterior.Thecoatingshouldpreservetheelasticityatlowtemperatures.

29

Suitable Expancel Products

Expancelmicrospheresarehighlyelastic,compressibleparticleswithlowspecificsurface,lowbinderdemandandlowwaterabsorptionbyvolume.Theyaregas-tightandretaintheirvolumeandsphericalformduringpreparation.

Expancel461WE40d36isrecommmendedastheprimarygradeforelasticwallandroofcoating;followedby461DET40d25-ifnotpossibletoaddthewaterthat461WE40d36contains.

Ifachlorinefreegradeisrequired,920DET40d25or921WE40d24isrecommended.

Grade 461WE40d36 461DET40d25 921WE40d25 920DET40d25

Appearance MoistenedPowder DryPowder MoistenedPowder DryPowder

Particlesizeaverageµm 30-50 30-50 35-55 35-55

Truedensityactive 36+3 25+3 24+3 25+3MS,kg/m3(lbs/gal)(0.3+0.025) (0.21+0.025) (0.2+0.025) (0.21+0.025)

Solidcontent(%) 15+2 >99 10+1.5 >99

Formulation of elastic wall and roof coating containing Expancel 461 WE 40 d36

TheformulationsbelowaimtobeaguideonhowthemainpropertiesofelasticwallandroofcoatingschangewhenExpancel461WEmicrospheresareincluded.

AddExpancel461WE40d36andremovethesameamountofmineralextender.Thiswillgive

unchangedviscositywhenadding1%byweightof461WE40d36.

Furtheradditionof461WE40d36decreasestheviscosity.Tomaintainthesameviscositylevelwith2%461WE40d36included,afurthersmalladditionofprimarythickenerisnecessary.

IncorporationofExpancel461DET40d25toelasticwallandroofcoatingswillsignificantly

30

Expancel461WE40d36Water Standard Content 1% 2% 90 90 88Orotan73125% 9 9 9TritonCF-10 2 2 2NopcoNXZ 3 3 3AcrysolRM-836.8% 13 13 13Propyleneglocol 16 16 14TioxideRCR-2 76 76 76Durcal5 250 240 230Expancel461WE40d36 -- 10 20Butylcarbitol 11 11 10SkaneM-8 2 2 2NopcoNXZ 3 3 3Acryliccopolymeremulsion,46% 465 465 465AcrysolASE60/Water1:1pH8 60 60 60

Constants and properties

Densityg/cm3(lbs/gal) 1.30(10.8)1.22(10.18)1.14(9.51)Solidcontent,weight% 56.5 55.6 55.0Solidcontent,volume% 41 44 46PVC% 35 43 49

increasetheviscosityandamorecarefulreformulationisnecessarytoachievesuitableconsistency.

ElasticwallandroofcoatingscontainingExpancelmicrospherescanbepreparedbymeansofaclosedlowspeedmixerordissolver.Usevacuumfordeaerationduringthelastpartofthemixing.

Theingredientsaretobeaddedinthesameorderasthetableshows.

Properties of elastic wall and roof coating containing Expancel 461 WE 40 d36

Water absorptionExpancel461WE40d36canreducethewateraborptionofelasticwallandroofcoating.Thewaterabsorption(mg/cm2)isplottedasthefunctionofthefilmthicknessatthreedifferentimmersions

Thepositiveeffectisclearlyshown.Coatingscontainingmicrospheresaremoreresistenttowatercomparedtocorrespondingcoatingwithoutmicrospheres.ThedifferenceinwaterabsorptionbetweenstandardcoatingandcoatingcontainingExpancelincreaseswithincreasingthickness.

Thisisimportantaselasticwallcoatingsareappliedatadrythicknessof1mmormore.

31

6

5

4

3

2

150 200 300250

0%1%

2%

Wat

era

bsor

ptio

nm

g/cm

2

Filmthickness,µm

Waterabsorptionofelasticwallandroofcoatingwithadditionof0to2%Expancel461WE40d36,1dayofimmersion

Water vapor permeabilityStudieshaveshownthatcoatingsincludingExpancel461WE40d36aremorepermeablethancoatingswithoutandthemicrospheressupportthetransportationofwatervapourthroughthematerial.Thetestisperformedbymeansofthecupmethodandthetruepermeabilitycoefficientsarecalculated.

Asthepermeabilitycoefficientsvarywiththefilmthicknessandthereareothersignificantresistancesthanthematerialinthesystem,theinverseofthepermeabilitycoefficientsareplottedagainsttheinverseofthethickness.

Extrapolationtoinfinitethicknesswillgivethetruepermeabilitycoefficientafterinversion.

TheinfluenceofExpancel461WE40d36onthewatervapourpermeabilitywouldprobablybemoreadvantageousduringtheageingofthecoating,asthetransportmechanismofwatervapourturnsfromactivateddiffusiontocapillaryflow.

32

x10-13

5

9

8

7

0% 2%1%

The

perm

eabi

lity

coef

ficie

nt

AdditionofExpancel461WE40d36

Truepermeabilitycoefficientkgnm/snm2nPaofelasticwallandroofcoatingwithadditionof0to2%Expancel461WE40d36

Low temperature flexibilityAccordingtotestmethodASTMD-1043,thelowtemperatureflexibilityofelasticwallandroofcoatingisnotaffectedbytheadditionofExpancel461WE40d36.Thedeterminedtemperatures(-28

oCto-29

oC/-18.4

oFto-20.2

oF)

areequalforstandardcoatingandcoatingscontainingExpancel.

Solid content by volumeAdditionofExpancel461WE40d36toelasticwallandroofcoatingswillincreasethesolidcontentbyvolume.Thatwillhelpwiththeformationofthicklayerstowhichthesetypesofcoatingsareapplied.

Tensile strengthTheelongationatbreakofwallandroofcoatingscontainingExpanceldecreasesonlyslightlycomparedtostandard.ThetensilestrengthalsodecreasessomewhatwhenExpancelmicrospheresareadded.Thesampleswerestoredfor10weeksatroomtemperaturebeforetesting.

High PVC-values with addition of Expancel 461 WE 40 d36ThegreatvolumecontributionfrommicrosphereswillresultinhighPVC-values,whichisquitemisleading,asExpancel461WE40d36consistsofhollowtightparticleswithalargevoidvolumethathasnodemandofbinder.

Stain resistanceTheelasticwallandroofcoatingisbasedonanacrylicco-polymeremulsion,whichisreticulableonsurfaceatthepresenceofnaturallight.Thereticulationprovidesahighstainresistance,whichismaintainedwhenExpancel461WE40d36isincluded.

33

Tensilestrength,MPa

5

9

8

7

0% 2%1%Elongation,%

Tensilestrengthofelasticwallandroofcoating(ISOR-527II)withadditionof0-2%Expancel461WE40d36.0%

1%2%

Other Acrylic Emulsions

Expancelmicrospheresgivemoderatechangesinthepropertiesofaformulationincludinganacrylicco-polymeremulsionwithsolidcontentof46%.Othermoreelasticacrylicemulsionswithhighersolidcontentareexpectedtogivethesameresult.BinderemulsionssuitableforthisapplicationarePrimalLT-2949andPrimalEC-3848ER.

Cost Savings

AdditionofExpancel461WE40d36tothistypeofcoatingwillgivepossibilitiesformaterialcostsavingsbyvolme.Byusing1%461WE40d36,anapproximatecostsavingwouldbe4-5%.

Correspondingapproximatecostsavingusing2%microspheresis8-9%.

34

Properties

ExpancelAddition 1% 2% 3%Waterabsorptionmg/cm2250µmdryfilmDays of immersion 1: 5.2 4.0 3.5 5: 4.6 3.8 3.3 15: 4.2 3.4 3.1Truepermeabilitycoefficientkgxm/m2nsnPa: 7.51013 8.81013 9.61013

Tensile strength MPA ISO R-537 II, +23oC (+73.4

oF)

Atmaximumstress 1.5 1.4 1.3Atbreak 1.4 1.3 1.1Elongation %Atmaximumstress 240 200 200Atbreak 390 370 330Elasticelongation 390 370 330

Chemical Description SupplierOrotan731 Dispersant Rohm&HaasTritonCF-10 Surfactant Rohm&HaasNopcoNXZ Defoamer Henkel-NopkoAcrysolRM-8 Thickener Rohm&HaasTioxideRCR-2 Titaniumdioxide TioxideDurcal5 Calciumcarbonate OmyaButylcarbitol Coalescent NotspecifiedSkaneM-8 Biocide Rohm&HaasAcrysolASE60 Thickener Rohm&HaasAcryliccopolymeremulsion Binder Rohm&Haas

Rawmaterialusedinsuggestedstartingformulation

35

10

Expancel® MicrospheresWaterborne Printing Inks

11

PrintinginkscontainingExpancelmicrospheresareformulatedtoproducethree-dimensionalprintsontextiles,wallpaper,paper,etc.Itcanalsobeusedtoachieveavelvetlookorothersurfaceeffect.

Thethree-dimensionaleffectisachievedbyheatingtheprinttoatemperatureatwhichthemicrospheresexpandandwhichcausesthebindertocrosslink.

Manyofthecommerciallyavailableprintinginksarealsosuitableforexpandableprintinginks.

FormulationBasicformulations,knownbyexperiencedprintersandinkmanufacturers,mayneedtobeslightlyadjustedduetotheadditionofmicrospherestoproduceraisedprintsonvarioussubstrates.

Abasicrecipecouldbe:

Expancel(dryweight)0-20partsperhundredBinder(s)40-60partsperhundredThickener2-35partsperhundred

Asaguide,theamountofdrybindershouldbeatleastthreetimestheamountofdrymicrospheresinordertogivegoodresistancetoabrasion.

However,themechanicalpropertiesofthebinderandalsotheexpansioncapacityofthegradeofExpancelhaveaninfluenceontheresistancetoabrasion.

37

Mixing Equipment

Nospecialmixingequipmentisrequired.

Bestresultsareachieved,however,withahomogenizersuchasaSilversonmixer.

Pigmentation

Printsmadefromunpigmentedinkhaveawhitesemi-opaqueappearance.

Byaddingupto10%byweightoftitaniumwhite,completelyopaquewhiteprintswillbeachieved.

Forcolouredprinting,addupto8%micro-pigmentdispersionsofnon-ioniccolours.

Components of the Printing Ink

BinderThebindershouldbehighlyelastic,giveagoodadhesiontothefabricandhavegoodwettensilestrength.

MicrospheresTherearedifferentgradesofExpancelfromwhichtochoosedependingontheheatingconditions:

642WU40- generalpurpose031WUF40- verygoodexpansion atlowtemperatures,inert,white007WUF40- verygoodexpansionatslightly highertemperatures,inert,white920WUF40- goodexpansionatveryhigh temperatures,inert,white.

Typicaldosagelevelsofmicrospheresare10-17%(dryweight)ofthetotalweightoftheformulation.Thegreatertheamountofmicrospheresthegreatertheloftoftheprint.

ExpancelWUFgradesarespecialgradeswhichcanbeusedinformulationswheretherheologicalstabilityisaproblem.ComparedtootherExpancelgrades,thedosageof031WUF40and007WUF40canbereducedby30-50%.

ThickenerThethickenershouldgiveashortbutteryrheology.Asuitablethickeneris,forexample,PrintofixThickernDSLiquid.

Auxiliary chemicalsGlycerineisahygroscopicagentandisaddedtopreventskinningandcloggingofscreens.FoamasterENA-515isaddedasadefoamer.WaterisaddedtocompensateforthevaryingsolidcontentofExpancel.

Inthefollowingformulationtheamountofthebinder(assolids)is26%byweight.Ifthispercentageisraised,anincreaseinstrengthand,possibly,inheightwillbegainedbutatthesametimetheinkdriesfaster,whichmaycausecloggingofthescreen.

TextilesIn a printing ink for textiles,

Expancel can help achieve effects such as a velvety look, puff effect

and the resemblance of embroidery.

38

Fixation

Duringfixation,thefollowingprocessestakeplace:

-dryingofthepaint-expansionofthemicrospheres-crosslinking/curingofthebinder

Thefixationtakesplaceindirectconnectionwiththeprintingat120-160

oC(248-320

oF).

Thetemperaturedependsonmicrospheregrade,substrate,typeofbinder,degreeofdepositandcuringoventobeused.

Fixationtakes1-3minutes,butcouldbeprolongedifacompletedrying/curingisnotobtainedwithinthistime.Theoptimumdrying/curingconditionsmaybetestedbytheprinter.

Incaseofmulti-colourprintingtheprintedmaterialisintermittentlydriedatroomtemperatureorupto80

oC(176

oF).

Intheeventofoverheatingand/orifatoolongheatingtimeisused,themicrospheresmaycollapseandbecomediscoloured.

Aninfrareddryermaybeusedinsteadof,orincombinationwith,aheatingoven.Alowertemperatureand/orashortertimeisthenrequired.

Textile Formulation

Amount in gPrimalECO-8(45.5%) 603.3Expancel642WU40(65%) 154-261.5Glycerine(100%) 40FoamasterENA-515(50%) 5H2O 174.9-67.4NH3(25%) approx3.5PrintofixThick,DSLiquid 19.3Total 1000g

Theviscosityoftheprintinginktendstoincreasewhenstored.

Procedure

Allingredients,exceptthickenerandammonia,aremixedusingahomogenisertoattainauniformmixture.AmmoniaisaddedtoadjustthemixturetoapHofapproximately8.5.Thethickenerisaddedtothemixtureduringstirring.Continuestirringuntilthickeningiscompleteandasmoothmixturehasbeenobtained.

Printing

Screenprintingandgravureprintingaresuitableapplicationtechniquesforexpandableprintinginks.Thethree-dimensionaleffectsbecomemostapparentwithaheavydeposit.

39

Components of the Printing Ink

BinderImportantpropertiesofthebinderareadhesionandresistancetoabrasion.Ahardbindercangivethedesiredresistancetoabrasionwhileaverysoft(andsticky)bindercanimprovetheadhesion.

AsuitablehardbinderisPrimalECO-16orequivalent.AsuitablesoftbinderisMowilithDM105orequivalent.

MicrospheresThereareseveralgradesofExpancelthataresuitableforwallpapers:

642WU40- generalpurpose031WUF40- verygoodexpansion atlowtemperatures,inert,white007WUF40- verygoodexpansionatslightly highertemperatures,inert,white920WUF40- goodexpansionatveryhigh temperatures,inert,white

TheamountofExpancelshouldbe1-15%(dryweight)ofthetotalweightoftheformulation.Thegreatertheamountofmicrospheresthegreatertheloftoftheprint.

Expancel031WUF40,007WUF40and920WUF40arespecialgradeswhichcanbeusedinformulationswheretherheologicalstabilityisaproblem.ComparedtootherExpancelgrades,thedosageof031WUF40and007WUF40canbereducedby30-50%.

ThickenerThethickenershouldgiveapseudoplasticrheology.Thiswillproducealowviscosityathighshearratesandwillallowprintingathighspeeds.Atthesametime,theviscositywillbehighatlowshearrates,preventingtheinkfromflowingafterprinting.

AsuitablethickenerisAcrysolRM-8;LyoprintPTXNisalsosuitableifamorepronouncedpseudoplasticityisdesired.

WallpaperFormulations suitable for printing

on wallpaper have been developed to achieve 3D and matting effects.

40

Ifpigmentsareaddedasadrypowder,theyshouldbeaddedandproperlydispersedin,forexample,thebindersbeforethemicrospheresareadded.Thereasonisthatitisgenerallymoredifficulttodispersepigmentsthanmicrospheres.

Itmightbenecessarytoaddadispersantinordertoobtaingooddispersionofthepigment.

Ifthepigmentisaddedasadispersionitcanbeaddedatanypoint.

Viscosity

Theprintinginkexhibitsapseudoplasticflowieitsviscositydecreaseswithincreasingshearrates.Regulateviscositybyusingmoreorlessthickenerintheformulation.

Pot Life

Storagedurabilityoftheaboveformulationisapproximatelyfourmonthswhenkeptinclosedcontainers.Apreservativecanbeaddedinordertopreventthegrowthofbacteriaandfungi.

Laboratorytestshavebeencarriedoutwithgoodresultsattheadditionof0.1-0.2%ActicideSPX.

Hydroscoping AgentGlycerineorpropyleneglycolcanbeusedtopreventskinningandcloggingofscreens.

DefoamerThedefoamerpreventsformationoffoamduringmixing.AsuitabledefoamerisFoamasterENA-515orequivalent.

WaterWaterisaddedtocompensateforthevaryingsolidcontentofExpancel.

Preparation

Micropheres,binders,hygroscopicagentanddefoamersaremixed.Bymeansofahighspeedmixer(homogeniser)themicrospheresarecompletelydispersedinthemixture.Caremustbetaken,however,thatthemixingdoesnottaketoolongsincedevelopedheatathighshearratesmaycauseprematureexpansionofthemicrospheres.

Thethickenerisaddedwhilethemixtureisbeingstirred.Continueagitationuntilasmoothmixtureisobtained.

Waterisaddedeitherasthelastcomponentorinthepre-mixtureofmicrospheres,binders,hygroscopicagentanddefoamer.

41

Screen Printing

Thethreedimensionaleffectsbecomemostapparentwithaheavydeposit.Thisisachievedbymeansofacoarsescreen,60-85mesh(24-34threadspercm).Byusingfinerscreensie100-125(40-50threads/cm)mesh,alowerdepositand,thereby,finepatternsandsharpcontours,areobtained.Itisrecommendedtofiltertheprintinginkbeforeapplicationtopreventcloggingofthescreen.

Drying

Drying,expansionandcuringarepreferablydoneimmediatelyafterprintingfor0.5-2minutes.Incaseofmulti-colourprinting,theprintedmaterialisintermittentlydriedat20-85

oC(68-185

oF).

Iftheprintisdriedbeforeexpansionthiswillproduceprintswithasmoothsurface.Iftheprintisexpandedwithoutdryingthiswillproduceprintswitharoughersurface.

Expansion and Curing

Thesuitabletemperatureforexpansionandcuringdependsonthemicrospheregradeaswellastheweightofthesubstrateandthedepositandmaybesetat120-180

oC(248-356

oF).

Theprintsthatwereusedtoproducetheexpansioncurvespresentedweredriedatroomtemperaturebeforetheywereexpandedinahotairoven.Theseexpansioncurvesmighthelpinfindingsuitableexpansiontimesandtemperatures.

Aninfrareddryermaybeusedinsteadoforincombinationwithaheatingoven.Alowertemperatureand/orashortertimeisthenrequired.

Intheeventofoverheatingand/orusingatoolongheatingtime,themicrospheresmaycollapseandbecomediscoloured.

Therecommendeddrying/curingconditionsmaybeadjustedbytheprinterdependingonsubstrate,degreeofdepositandthecuringoventobeused.

42

Effect on surface roughness when drying before expansionThesurfaceofaprintthatisheatedandexpandedimmediatelyafterprintingmaybecomesomewhatroughbecauseofwatervapour.

Ontheotherhand,iftheprintisfirstdriedatatemperaturewhichistoolowtostarttheexpansionthesurfaceoftheexpandedprintwillbesmoother.

Surface Modification

Byusingmicrosphereswithdifferentparticlesizes,thelookandfeeloftheprintedsurfacecanbemodified.

43

Expancel920WUF40

Expancel930DU120

Printdriedbeforeexpansion,SEM20x

Printnotdriedbeforeexpansion,SEM20x

Wallpaper Formulations

WallpaperformulationwithExpancel642WU40usingMowilithDM105andPrimalECO-16asbindersandLyoprintPTXNasthickener.

Solids Amount % (g) (oz)MowilithDM105 55.0 407.8 14.4PrimalECO16 45.5 335.6 11.8Expancel642WU40 67.5 88.9 3.13Glycerine 100.0 50.0 1.76FoamasterENA-515 50.0 8.0 0.28LyoprintPTXN 90.0 10.0 0.35Water 0.0 99.7 3.52Total 50.01000.0 35.3

Partofnon-volatilesbeingbinders:75.4%Partofnon-volatilesbeingmicrospheres:12%Binder/microspheres(solids/solids):6.28

44

Expansionfactor[x]after60sexpansion

Temperature[oC]

45

Suppliers of Chemicals

Chemical Agent SupplierPrimalECO-8 Acrylicemulsionbinder RohmandHaas

PrimalECO-16 Methylmethacrylate/ethlyacrylatemulsionbinder RohmandHaas

MowilithDM105 Vinylacetate/ethylenecopolymerdispersionbinder CelaneseEmulsions

PrintofixThickenerDSLiquid Syntheticthickenerbasedonammoniumpolyacrylate Clariant

LyoprintPT-XN Acrylicpolymerdispersion Huntsman

AcrysolRM-8 Polyurethanethickener RohmandHaas

FoamasterENA-515 Mineraloilbaseddefoamer Cognis

ActicideSPX Preservative ThorChemicals

ParticleSize TrueDensity SolventExpancel µmD(0.5) kg/m3 Resistance

551DE40d42 30-50 42+4 3461DE20d70 15-25 70+6 4461DE40d60 20-40 60+5 4461DET40d25 35-55 25+3 4920DE40d30 35-55 30+3 5920DET40d25 35-55 25+3 5

Specification

ProductSpecificationforExpancel®microspheres

Expancel DEDryExpandedMicrospheres

46

Est.ParticleSize Solid TrueDensity True SolventExpancel µmD(0.5) Content kg/m3 Volume Resistance

461WE20d36 20-30 15+2 36+4 4.2+0.45 3461WE40d36 30-50 15+2 36+4 4.2+0.45 3921WE40d24 35-55 10+1.5 24+3 4.2+0.45 5

Expancel WEWetExpandedMicrospheres

Expancel DUDryUnexpandedMicrospheres

ParticleSize ThermomechanicalAnalysis SolventExpancel µmD(0.5) Tstart

oC Tmax

oC Densitykg/m3 Resistance

551DU40 10-16 95-100 139-147 <17 3461DU20 6-9 100-106 137-145 <30 4461DU40 9-15 98-104 142-150 <20 4051DU40 9-15 108-113 142-151 <25 4031DU40 10-16 80-95 120-135 <12 3053DU40 10-16 96-103 138-146 <20 3093DU120 28-38 120-130 188-203 <6.5 5909DU80 18-24 120-130 175-190 <10 5920DU40 10-16 123-133 168-178 <17 5920DU80 18-24 123-133 180-195 <14 5920DU120 28-38 122-132 194-206 <14 5930DU120 28-38 122-132 191-204 <6.5 5950DU80 18-24 138-148 188-200 <12 5951DU120 28-38 133-143 190-205 <9 5

47

ParticleSizeD(0.5): 28-38µm ThermomechanicalAnalysis: Tstart 122-132

oC

Tmax 194-206oC

TMA-density <14kg/m3

ResidualSubstances:Acrylonitrile <30mg/kgMethacrylonitrile <100mg/kgSodium2-cyanoethanesulfonate <200mg/kgSulfite <2000mg/kg

Expancel FG92 DUX 120DryUnexpandedMicrospheres

Expancel MBMasterbatchwithUnexpandedMicrospheres

Heightof BulkDensityExpancel Grade Concentration Carrier Foaming(mm) (g/l)

920MB120 920-120 65+1 EVA* 90-140 400-500 (200

oC)

930MB120 930-120 65+1 EVA* 100-150 400-500 (200

oC)

950MB80 950-80 65+1 EVA* 90-130 400-500 (210

oC)

951MB120 951-120 65+1 EVA* 100-150 400-500 (210

oC)

EVA*-Co-polymerofethylenevinylacetate

48

Expancel WUWetUnexpandedMicrospheres

DryContent ParticleSize ThermomechanicalAnalysis Expancel % µmD(0.5) Tstart

oC Tmax

oC Densitykg/m3

551WU40 71+2.5 10-16 95-100 139-147 <17461WU20 68+2.5 6-9 100-106 137-145 <30461WU40 68+2.5 9-15 98-104 142-150 <20007WU40 71+2.5 10-16 91-99 138-143 <15031WUF40 76+2.5 10-16 80-95 120-135 <12053WU40 71+2.5 10-16 96-103 138-146 <20920WUF40 71+2.5 10-16 123-133 170-180 <17

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Boud Minerals ABHåkantorpsvägen109SE-26391HöganäsSwedenTel:+4642333741Fax:+4642333829Web:www.boud.comEmail:sweden@boud.com

Boud Minerals LimitedWestBankSuttonBridgeLincolnshirePE129URUKTel:+44(0)1406351988Fax:+44(0)1406350897Web:www.boud.comEmail:sales@boud.com B