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DOI:10.1126/science.1075707,976(2002);297Scienceetal.RobertR.Matheson,Jr.,SoftCoatings20th-to21st-CenturyTechnologicalChallengesinThiscopyisforyourpersonal,non-commercialuseonly.clickingherecolleagues,clients,orcustomersby,youcanorderhigh-qualitycopiesforyourIfyouwishtodistributethisarticletoothers.herefollowingtheguidelinescanbeobtainedbyPermissiontorepublishorrepurposearticlesorportionsofarticles(thisinformationiscurrentasofMarch23,2010):T/cgi/content/full/297/5583/976versionofthisarticleat:includinghigh-resolutionfigures,canbefoundintheonlineUpdatedinformationandservices,foundat:canberelatedtothisarticleAlistofselectedadditionalarticlesontheScienceWebsites/cgi/content/full/297/5583/976#related-content7article(s)ontheISIWebofScience.citedbyThisarticlehasbeen/cgi/collection/mat_sciMaterialsScience:subjectcollectionsThisarticleappearsinthefollowingregisteredtrademarkofAAAS.isaScience2002bytheAmericanAssociationfortheAdvancementofScience;allrightsreserved.ThetitleCopyrightAmericanAssociationfortheAdvancementofScience,1200NewYorkAvenueNW,Washington,DC20005.(printISSN0036-8075;onlineISSN1095-9203)ispublishedweekly,exceptthelastweekinDecember,bytheScienceonMarch23,2010DownloadedfromwhereRisthereflectanceofthesample,H9270isthedistanceonthesurfacebetweentwopoints,H9275istheangularfrequency,kisthewavenumber,fisthefocallengthoftheincidentradiation,andH9268isthermsheightofthesurface.A2DanalysisoftheopticshasbeencarriedoutbyOgilvy(35).Whitehouseconcluded(34)(forundulationswithlengthscalegreaterthanthewavelengthoftheincidentradiation)thatthesurfaceappearedglossyiftheprobabilitydensityoftheslopesonthesurfacewasstrictlyconfinedtoanarrowangle.Biocompatibility.Finally,biologicalinterac-tionswithasurfacehavealsobeenfoundtodependonitstopography.AgoodreviewofthetopologicalcontrolofcelladhesionandactivityonasurfacehasbeenmadebyCurtisandWilkinson(36),andamoregeneralreviewoftheroleofpolymerbiomaterialsmayalsobefound(37).Suchconsiderationsarerelevantforanumberofinvivoandinvitroapplications,suchasbiologicalsensors,hipreplacements(38),andmorecomplextissueimplantssuchasreplacementbone,wherethegrowthofcellswithintheartificialstructureistobeencour-aged.Forexample,thesizeandmorphologyofcrystalsatthesurfaceofoctacalciumphos-phatecoatedcollagenhavebeenshowntoaf-fecttheinteractionofcellswiththesurface,asillustratedinFig.4.Thelargerscaletopographywasfoundtoleadtolessfavorablespheroidalcellsthatformedfewerintercellularconnections(39).Insomecases,thetopographyofasurfacemaybecarefullycontrolledtopromotecelladhesion(40,41).ConclusionThetopographyofasurfaceisadirectresultofthenatureofthematerialthatdefinesit.Theanalysisofthetopographyofasample,madepossibleonthenanoscalebythedevel-opmentofAFMtechniques,needstobecare-fullyconsideredinordertorelatethecom-plexityofa2Dsurfacetothematerialsproperties.Theresultwillbethebettercon-trolofanumberofproperties,suchasopticalfinish,andoftheinteractionofasurfacewithasecondarymaterial,whetherthatbeanad-hesive,asecondarycomponentofacompos-ite,orabiologicalspecies.ReferencesandNotes1.J.D.Afnitoetal.,ThinSolidFilms291,63(1996).2.J.A.DeAro,K.D.Weston,S.K.Buratto,U.Lemmer,Chem.Phys.Lett.277,532(1997).3.Y.Nabetani,M.Yamasaki,A.Miura,N.Tamai,ThinSolidFilms393,329(2001).4.M.Sferrazzaetal.,Phys.Rev.Lett.78,3693(1997).5.E.Schaffer,T.Thurn-Albrecht,T.P.Russell,U.Steiner,Europhys.Lett.53,218(2001).6.D.G.Bucknall,G.A.D.Briggs,MRSSymp.Ser.:Nanopatterning:Ultralarge-ScaleIntegrationBio-technol.705,151(2002),L.Merhari,K.E.Gonsalves,E.A.Dobisz,M.Angelopulss,D.Herr,Eds.7.S.Walheim,E.Schaffer,J.Mlynek,U.Steiner,Science283,520(1999).8.J.Heier,E.Sivaniah,E.J.Kramer,Macromolecules32,9007(1999).9.T.Thurn-Albrecht,J.DeRouchey,T.P.Russell,Mac-romolecules33,3250(2000).10.A.Karimetal.,Macromolecules31,857(1998).11.X.P.Jiang,H.P.Zheng,S.Gourdin,P.T.Hammond,Langmuir18,2607(2002).12.G.Goldbeck-Woodetal.,Macromolecules35,5283(2002).13.V.N.Bliznyuk,K.Kirov,H.E.Assender,G.A.D.Briggs,Polym.Preprints41,1489(2000).14.F.Dinelli,H.E.Assender,K.Kirov,O.V.Kolosov,Polymer41,4285(2000).15.C.Rauwendaal,PolymerExtrusion(Hanser,Munich,1985).16.S.-J.Liu,Plast.RubberComposites30,170(2001).17.B.Monasseetal.,Plast.ElastomeresMag.53,29(2001).18.Y.Oyanagi,Int.Polym.Sci.Technol.24,T38(1997).19.A.Guinier,X-rayDiffractioninCrystals,ImperfectCrystals,andAmorphousBodies(W.H.Freeman,SanFrancisco,1963).20.V.N.Bliznyuk,V.M.Burlakov,H.E.Assender,G.A.D.Briggs,Y.Tsukahara,Macromol.Symp.167,89(2001).21.W.M.Tong,R.S.Williams,Annu.Rev.Phys.Chem.45,401(1994).22.P.Meakin,Fractals,ScalingandGrowthFarfromEquilibrium(CambridgeUniv.Press,Cambridge,1998).23.C.M.Chan,T.M.Ko,H.Hiraoka,Surf.Sci.Rep.24,3(1996).24.E.M.Liston,L.Martinu,M.R.Wertheimer,J.AdhesionSci.Technol.7,1091(1993).25.Q.C.Sun,D.D.Zhang,L.C.Wadsworth,TappiJ.81,177(1998).26.V.Bliznyuketal.,Macromolecules32,361(1999).27.N.Zettsu,T.Ubukata,T.Seki,K.Ichimura,Adv.Mater.13,1693(2001).28.R.S.Hunter,R.W.Harold,TheMeasurementofAppearance(Wiley,NewYork,ed.2,1987).29.H.Davies,Proc.Inst.Electr.Eng.101,209(1954).30.F.M.Willmouth,inOpticalPropertiesofPolymers,G.H.Meeten,Ed.(Elsevier,Amsterdam,1986).31.D.Porter,GroupInteractionModellingofPolymerProperties(MarcelDekker,NewYork,1995).32.P.Beckmann,A.Spizzichino,TheScatteringofElec-tromagneticWavesfromRoughSurfaces(Pergamon,NewYork,1987).33.K.Porfyrakis,N.Marston,H.E.Assender,inpreparation.34.D.J.Whitehouse,Proc.Inst.Mech.Eng.B:J.Eng.Manuf.207,31(1993).35.J.A.Ogilvy,TheoryofWaveScatteringfromRandomRoughSurfaces(AdamHilger,Bristol,UK,1991).36.A.Curtis,C.Wilkinson,Biomaterials18,1573(1997).37.L.G.Grifth,ActaMater.48,263(2000).38.T.M.McGloughlin,A.G.Kavanagh,Proc.Inst.Mech.Eng.PartHJ.Eng.Med.214,349(2000).39.A.C.Lawsonetal.,MRSSymp.Ser.:Biomed.Mater.:DrugDelivery,ImplantsTissueEng.550,235(1999),T.Neenan,M.Marcolongo,R.F.Valentini,Eds.40.C.S.Ranucci,P.V.Moghe,J.Biomed.Mater.Res.54,149(2001).41.P.Banerjee,D.J.Irvine,A.M.Mayes,L.G.Grifth,J.Biomed.Mater.Res.50,331(2000).42.TheauthorsacknowledgecontributionstothisworkfromA.Briggs,D.Bucknall,V.Burlakov,J.Czernuska,andS.WilkinsonfromOxfordUniversity;N.MarstonandI.RobinsonfromLuciteInternational;andY.TsukaharafromtheToppanPrintingCompany.VIEWPOINT20th-to21st-CenturyTechnologicalChallengesinSoftCoatingsRobertR.MathesonJr.Coatingsareamongthemostancienttechnologiesofhumankind.Rela-tivelysoftcoatingscomprisingorganicmaterialssuchasblood,eggs,andextractsfromplantswereinusemorethan20,000yearsago,andcoatingactivityhasbeencontinuouslypracticedsincethenwithgraduallyimprov-ingmaterialsandapplicationtechniques.Thefundamentalpurposesofprotectingand/ordecoratingsubstrateshaveremainedubiquitousacrossallthecenturiesandculturesofcivilization.Thisarticleattemptstoextrapolatethelongtaleofchangeinsoftcoatingtechnologyfromitscurrentstatebyidentifyingsomekeyproblemsthatattractresearchanddevelopmenteffortsasour21stcenturybegins.Humanshavebeendecoratingandprotectingvarioussurfacesformanythousandsofyears.Oneveryusefulwayofaccomplishingeitherorbothofthosetasksistoapplyathinlayerofsomenewmaterialwithappropriatechar-acteristics(ofappearance,durability,adhe-sion,andapplicationrequirements)directlyontothesurfaceofinterest.Thatnewmaterialisacoating.Understandably,theearlyhistoryofcoatingsisastoryofveryspecialized,oftenuniquematerialcombinations,astrialanderrorachievedgoalswithonlythemate-rialsathandinnature.Thisheritageofcus-tomizationisstilldetectableinthemoderncoatingsworld,whichdemandsatremendousamountfromthematerialsoftensyntheticbutsomestillcontainingormadeofnaturalproductstobethinlyappliedonasurface.Theyneedtobeeasilyanduniformlyapplied;setupwithinareasonableamountoftimeandprocessconstraints;haveaminimalenviron-mentalimpactintheirsynthesis,combina-DuPontPerformanceCoatings,950StephensonHigh-way,Troy,MI48083,USA.E-mail:9AUGUST2002VOL297SCIENCE976MATERIALSSCIENCE:SOFTSURFACESonMarch23,2010Downloadedfromtion,andapplication;resisttheeffectsofenvironmentalassault;andprovidegoodeco-nomicvalue.Iexaminefiveimportantforcesthataredrivinghowsuchcoatingsaremadeandimprovedtoday.NomenclatureThelong,decentralized,andempiricalevo-lutionofcoatingmaterialsandprocesseshasleftbehindanarcaneandfrequentlyconfus-ingvocabulary(1).Itwillbehelpfultodefinethreetermsthatarefrequentlyusedbutalsoareindiscriminatelyinterchanged.Alacquer(fromtheArabicwordlakk)isacoatingthatformsonasurface(frequentlybyevaporationofsolvents)withouttheinterventionofcova-lentbondsformingbetweenthefilm-formingingredients.Incontrast,avarnish(fromtheMedievalLatinvernice)isacoatingthatessentiallyrequireschemicalreactionsbe-tweenfilm-formingingredientsduringacur-ingprocessafteritsapplicationtoasubstrate.Enamels(fromtheGermanicesmail)areaverycommonsubsetofvarnishes,whichuseaheating(stoving)steptocarryoutthecur-ingprocess.Theseclassificationsweresharpanddistinctinthepast,butcurrentdevelop-mentsarebeginningtoweakentheirclarity.However,theywillbeusefulhereinhigh-lightingtheparticularchallengesfacingcoat-ingdevelopment.MinimizingtheEnvironmentalFootprintOneofthemostcommonlyrecognizedchal-lengesisthereductionoreliminationofvol-atileorganiccompounds(VOCs)fromtheformulationsofmoderncoatings(2).Inthequantitiesgeneratedbytodayspopulationandparticularlyintheconcentrationspro-ducedinindustrializedurbanenvironments,VOCemissionscontributetoairpollutionproblems.Clearly,thisproblemismostacuteforlacquers.Themutuallyunreactivecom-ponentsofalacquerabsolutelydependonsomeprocessingaid(commonlyasolvent)tomakethemmalleableenoughforapplica-tion,andthoseaidsmustthenberemovedtoleavethecoatingrobustenoughtoprotectanddecorate.Solventminimizationfindsitsultimateexpressioninlacquerversionsofpowdercoatings,wheresolventsarereplacedwithheat,whichisusedtoapplythecoating.Uponcooling,thepropertiesthatdevelopcansometimesbeadequatetothetaskathand.However,theseproductsarelimitedinthatifthecoatingisheatedtoatemper-aturewhereitsapplicationispossible,thenitwillsoftenanddeformonceagain.More-over,becausemostcoatingfilmsareeitheramorphousorsemicrystalline,theirabilitytoretainaminimumhardnessandtoresistsustainedloadsbeginstofalloffquiteno-ticeablyattemperatureswellbelowthosewhererapidflowandlevelingareachieved(3).Acceptablesolventsubstitutionbasicallyamountstousingtheliquidformofsubstanc-esthatarenaturallypresentasgasesintheatmosphere(suchaswaterandcarbondiox-ide).Liquidorsupercriticalcarbondioxideislimitedtoindustrialapplicationsbecauseoftherequirementsforhighpressure.Wateriseasiertousewidelyasacoatingsolvent,butitisnotapanacea.Oneexampleofaproblemthatcomeswithwateristheinevitablywidevariationindryingtimesthataccompaniesapplicationinenvironmentsofdifferentrel-ativehumidity.Becauserelativehumiditycanchangealmosthourly,thisisaseriouscomplication.Infact,virtuallyallwaterbornecoatingstodaycontainquitesubstantiallevelsoforganic“cosolvents.”TheVOCcontentofwaterbornecoatingsisgreatlyreducedascomparedtothatofolder,conventionalsolvent-bornecoatings,butitisnotfullyeliminated.Amajoractivityinmoderncoat-ingdevelopmentisthesearchforbalancedchemistrythatwillpushbacktheselimitsonenvironmentallymorefavorablelacquerswhileretainingtheattractivesimplicity,thesyntheticcontrol,andthelowcostofthetechnology.VOCreleaseisnottheonlyenvironmen-talimpactfactorthatisimportantfordrivingchangeincoatingtechnology.IntheUnitedStates,regulationsonso-calledhazardousairpollutants(HAPs)areimportant(4).Thisisanexplicitlistofsolvents,typicallyaromatic,thatareusedinlargequantitiesandareeitherknowntocauseorsuspectedofcausinghu-manhealthproblemswithchronicexposure.Avarietyofother,similarlylocalconstraintsforparticularingredientsexistaroundtheglobe.Oneverywidelyexperiencedrestric-tionisthatonheavymetals.Therearemanyhistoricalexampleswherefairlylargeamountsofparticularmetalshavefounduseinsoftcoatings(5).Someexamplesaretheuseofleadforanticorrosionincathodicelec-trocoatcoatings,ofhexavalentchromiuminmetalcoatings,ofbothleadandcadmiuminvariouspigments,ofdivalenttininantifoul-ingmarinecoatings,andevenofmercuryasanantifungalagentforsomeinteriorpaints.Incommonwithotherareasofmaterialsprocessing,coatingtechnologynowhastolookforalternativeingredientswithoutun-controllable,long-termenvironmentalconse-quences.Nosimilarlygeneraltechnicalsolu-tionshaveyetbeenfound,althoughprogressisbeingmade,particularlywithrespecttoanticorrosioncoatings.BeatingBacktheEnvironmentChemicalandmechanicalresistancetoenvi-ronmentalinsultisacommonfeatureofmanycoatingsystemsandakeyreasonfortheirapplication.Biologicalattacksareclas-sicproblemsencounteredovertheyears,andtheircatalogdefinesthecurrentfrontier.Un-derwatercoatingsthatcanresisttheattach-mentanddegradationofaqueousorganisms(suchaswormsandbarnacles)areneededforshippingandforstructures.Exteriorcoatingsthatcanresistparticularinsect,bird,andplantexcretionsarefrequentlyneededinlo-calgeographies.Interiorcoatingsthatcanresistmildew,otherfungaldamage,molds,andbacteriaarefrequentlydesired.Thegen-eralchallengeisnearlyalwaysthesame:specificresistancetoadefinedclassofbio-logicalinsultwithoutnonspecifictoxicityorirritation.Itisnaturaltoworktowardthissetofobjectiveswithadditivestailoredtoeachtask.Experienceshowsthisnaturalpathtobeexpensiveandusuallyimperfect,butocca-sionallyfruitful.Still,itisprobablyfairtosaythatnoexamplesexistwheretheperformanceofthebroadlytoxic,heavymetalbasedad-ditiveshasbeenachievedwiththemorespe-cificmoderntools.AnewideaistoproducecounteragentsinsitubytappingthechemicalreactionsthatmustaccompanybiologicalattackorevensimpleweatheringintheactiveenvironmentsnearEarthssurface(6).Forexample,bio-logicaldamagemaybeaccompaniedbyhy-drolyticscissionofcoatingcomponents.Ifthosecanbedesignedtohydrolyzeintoanti-septic,antifouling,oranti-whateverproductstailoredtothetask,thenperhapsaneffectivesolutioncanbefound.MaximizingControlThroughMolecularArchitecturesItisimportanttolookbeyondenvironmentalattackonthecoatingitself.Theclassicalroleofcoatingsistoprotectsomethingelsefromtheenvironment.Thisprotectioncanbeme-chanicalorchemicalinnature.Varnisheshavebeendevelopedparticularlyforthesepurposes,becauseinsituor“onthework”cross-linkingisaveryeffectivetechniqueforaugmentingthecoatingsmaterialpropertieswhileavoidingcompromisesinapplication.Anextremelyactiveareaofdevelopmentinmoderncoatingsisdirectedtoimprovingthecontrolofsuchreactions.Inevitably,thesemustbecarriedoutinavarietyofworkenviron-ments.Nearoneextremearecoatingsusedincontrolledchambers,asfortheradiationorthermalcuringofacoatingusedtosealaconnectionbetweenelectroniccomponents.Thevariablesofconcernmaybefilmthicknessatvariouspoints,surfacecleanliness,andsmalltemperaturegradientsarisingfrommaterialsofdifferentthermalconductivity.Neartheotherextremearethegrosslyfluctuatingenviron-mentsthatcanbefoundinarailroadlocomo-tiveshed,wherehumidity,temperature,airflow,applicationrate,surfacepreparation,andmaybeevensurfacematerialareallvariables.OSCIENCEVOL2979AUGUST2002977MATERIALSSCIENCE:SOFTSURFACESonMarch23,2010Downloadedfromtotakegreatcareinsynthesizingthevar-nishingredientssothatnoespeciallytrou-blesomereactionscaneveroccur.Somesidereactionsareunderstandablymoredel-eteriousthanothers,andthegoalistoleavenoopportunityforthemosttroublesome,nomatterwhatconditionsmightappear.Thisleadstotheuseofcontrolledpolymer-izationtechniquesexemplifiedbutcertain-lynotlimitedtogrouptransferpolymeriza-tion(7)foracrylicmaterials,rigorousexclusionofnonfunctional(unabletopar-ticipateincuring)matrixmaterials,andoptimizingmolarmassdistributionstoavoiduntimelyimmiscibilityduringcureandsimilarstrategies.Thespecificfieldofautomotivecoatinghasbeeninthefore-frontofthisactivitybecauseoftheex-tremelyhighperformancestandardsandpowerfuleconomicincentivesfoundinmass-producingautomobiles.Someofthenewsyntheticandanalyticaltechniquesbe-ingintroducedforcontrollingandmonitor-ingautomotiveenamelshavebeende-scribed(8).Decorativecoatingsinparticularneedtoincorporatepigments,dyes,reflectivemetal,andmicaflakesformanyapplications.Onecommontechniqueforeffectivelydistribut-ingsuchparticlesistocovertheirsurfaceswithdispersantsthataidintheirdispersioninthebulkofthecoatingandpreventreagglom-erationunderthevarietyofcircumstancesthatmightariselater.Exquisitecontrolofthemolecularstructureisneededinordertoachievegooddistributionoftheparticles,minimalmobilityonceappliedtoasurface,theabilitytoresistforcesthatdrivere-agglomeration,andcompatibilitywiththebulkcoatingandyetnotinduceproblemswithadhesion,application,orlong-termper-formance.Becausepigmentsareveryfre-quentlythemostexpensiveingredientsinadecorativecoating,itisimportanttousethemefficiently.Additionally,assolventconcen-trationandvarietyaredecreasedbecauseoftheenvironmentalpressurespreviouslycited,opportunitiesformanagingdispersionprob-lemsbymodifyingthecoatingmedium(thecoatingvehicle)decrease.Smallwonderthatthechemistryusedtomakemoderndispers-antsprovidesanexceptionallyclearpictureofthestateoftheartinmolecularcontrolincoatings.Techniquesformakingblockco-polymers(eachblockdesignedforaffinitytoeitherasurfaceorthesolventenvironment)havebeendevelopedandcommercializedandarestillbeingimproved.Thepatentartisextensiveandgrowing,butthatfromC.Ho-sotte-Filbert(9)isarepresentativeexample.FunctionalCoatingsAfourthmodernfrontierintheworldofsoftcoatingscanbedescriptivelycalled“postcurereactivity”forvarnishes,orperhaps“in-usereactivity”forlacquers.Suchreactionshavebeenrecognizedforalongtimeinexamplessuchasthelong-termoxidationofalkydvar-nishesandmanylacquersbasedonnaturalproducts.Historically,thesehavebeenviewedastroublesomeinstabilities.Howev-er,ithasbeenlearnedthatsomeinstancesofpostcurechemistryhaveadvantages,withoneexamplebeingtheslowcondensationandinterchangeofsiloxanebondsinorganosilaneenamels(10).Thesecanacttorelaxstressesthatotherwisegrowuncompensatedinlight-andoxidation-stressedexteriorcoatings.Het-erogeneouscoatingsthatreacttocracksorfracturesbyreleasingpostcurerepairingre-dientshavebeenpostulated(11).Evenmoresophisticatedusesincon-trolledreleaseorothertransportcontrolprob-lemscanbesketchedtoday.Itshouldbenotedthatagreatmanyinstancesexistinwhichcoatingsareusedtomanipulate(gen-erallytoretard,delay,orprevent)thetrans-portandexchangeofmaterials.Atmosphericoxygencontactingfood,carbondioxideexit-ingcarbonatedbeverages,thereleaseofpharmaceuticalsintothebody,electricalchargeleakingintoadevicecomponent,heatexitinganisothermalenvironment,orwaterandionicmaterialscontactingcorro-sion-susceptiblemetalsareexampleswherethetransportcharacteristicsofcoatingsareimportantindeterminingperformance.Thelong-termcapabilityofacoatingtoim-proveorattheleastreacttocompensateforadecliningtransportcharacteristicmaybejustasusefulasthesameabilitytooffsetdecliningmechanicalcharacteristics.IndustrialScaleChallengesAfinalclassofproblemsdrivinginnovationinmoderncoatingscanbefoundinthecostsandlimitationsoftheheatingstepinenamelprocessing.Notsurprisingly,theseproblemsincludethecapitalandenergycostsassociat-edwithheatingobjectswithlargethermalmasses,damagetoheat-sensitivesubstrates,andtheinventoryproblemsthataccumulatewithlongcycletimesinanyprocess.Themostdirectapproachistoreducetherequiredbakingtemperatureand/ortime.Thereisscopeherefornovelchemicalreactionsandcatalystinnovations,bothofwhichcommandattentiontoday.Alternatively,ifthecuringreactionscanbeactivatedbyamechanismotherthansimpleheating,thenproblemscanbeminimizedwithoutlosingthecure-in-ducedimprovementsincoatingperformance.Muchcurrentworkisdirectedtoradiation-curable(withultravioletlight,electronbeams,andevenvisiblelight)coatingsandeffortstoextendtheircurrentembodimentstocomplexarticlesandlong-termuse(12).Powdercoatingsandliquidcoatingsarebothobjectsofstudyandinnovation.Themajorchallengefacedinsuchdevelopmentarisesfromlimitationsontheuniformityofcureforincompletelytransparentcoatings(shadowedareasdonotreceivethesamefluxofradia-tion)orcoatingsoncomplexshapes.Examplesofspecificnewproductsarisinginresponsetooneoranotherofthesefivegeneraldevelopmentareascanbefoundinmanyplacesandfrommanydevelopmentlab-oratories.

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