Hansen Solubility Parameters： A User's Handbook.pdf

Hansen Solubility Parameters： A User's Handbook.pdf

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HANSENSOLUBILITYPARAMETERSAUsersHandbookSecondEdition7248_C000.fmPageiThursday,May24,20071:

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40PMHANSENSOLUBILITYPARAMETERSAUsersHandbookSecondEditionCharlesM.Hansen7248_C000.fmPageiiiThursday,May24,20071:

40PMCRCPressTaylor&FrancisGroup6000BrokenSoundParkwayNW,Suite300BocaRaton,FL33487-27422007byTaylor&FrancisGroup,LLCCRCPressisanimprintofTaylor&FrancisGroup,anInformabusinessNoclaimtooriginalU.S.GovernmentworksPrintedintheUnitedStatesofAmericaonacid-freepaper10987654321InternationalStandardBookNumber-10:

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978-0-8493-7248-3（Hardcover）Thisbookcontainsinformationobtainedfromauthenticandhighlyregardedsources.Reprintedmaterialisquotedwithpermission,andsourcesareindicated.Awidevarietyofreferencesarelisted.Reasonableeffortshavebeenmadetopublishreliabledataandinformation,buttheauthorandthepublishercannotassumeresponsibilityforthevalidityofallmaterialsorfortheconsequencesoftheiruse.Nopartofthisbookmaybereprinted,reproduced,transmitted,orutilizedinanyformbyanyelectronic,mechanical,orothermeans,nowknownorhereafterinvented,includingphotocopying,microfilming,andrecording,orinanyinforma-tionstorageorretrievalsystem,withoutwrittenpermissionfromthepublishers.Forpermissiontophotocopyorusematerialelectronicallyfromthiswork,pleaseaccess（http:

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ausershandbook.-2nded./editedbyCharlesHansen.p.cm.Rev.ed.of:

Hansensolubilityparameters/CharlesM.Hansen.c2000.Includesbibliographicalreferencesandindex.ISBN0-8493-7248-8（alk.paper）1.Solution（Chemistry）2.Polymers-Solubility.3.Thinfilms.I.Hansen,CharlesM.II.Hansen,CharlesM.Hansensolubilityparameters.QD543.H2582007547.70454-dc222006051083VisittheTaylor&FrancisWebsiteathttp:

/andtheCRCPressWebsiteathttp:

/7248_C000.fmPageivThursday,May24,20071:

40PMContributorsDr.JohnDurkeeConsultantinCriticalandMetalCleaningHunt,TexasU.S.A.Dr.techn.CharlesM.HansenConsultantHoersholm,DenmarkProf.GeorgiosM.KontogeorgisTechnicalUniversityofDenmarkDepartmentofChemicalEngineeringLyngby,DenmarkProf.CostasPanayiotouDepartmentofChemicalEngineeringUniversityofThessalonikiThessaloniki,GreeceTimS.PoulsenSr.ResearchScientistMolecularPathologyGlostrup,DenmarkDr.rer.nat.HannoPriebeSr.ResearchScientistChemicalDevelopmentProcessResearchGEHealthcareAmershamHealthASOslo,NorwayPerRedeliusResearchManagerNynasBitumenProductTechnologyNynashamn,SwedenProf.LaurieL.WilliamsDepartmentofPhysics&EngineeringFortLewisCollegeDurango,ColoradoU.S.A.7248_C000.fmPagevThursday,May24,20071:

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40PMPrefacetotheFirstEditionMyworkwithsolventsstartedinDenmarkin1962whenIwasagraduatestudent.ThemajorresultsofthisworkweretherealizationthatpolymerfilmformationbysolventevaporationtookplaceintwodistinctphasesandthedevelopmentofwhathascometobecalledHansensolubility（orcohesion）parameters,abbreviatedinthefollowingbyHSP.Thefirstphaseoffilmformationbysolventevaporationiscontrolledbysurfacephenomenasuchassolventvaporpressure,windvelocity,heattransfer,etc.,andthesecondphaseiscontrolledbyconcentration-dependentdiffusionofsolventmoleculesfromwithinthefilmtotheairsurface.Itisnotcontrolledbythebindingofsolventmoleculestopolymermoleculesbyhydrogenbondingaswaspreviouslythought.Mysolubilityparameterworkwasactuallystartedtodefineaffinitiesbetweensolventandpolymertohelppredictthedegreeofthisbindingwhichwasthoughttocontrolsolventretention.Thiswasclearlyafutileendeavorastherewasabsolutelynocorrelation.Thesolventswithsmallerandmorelinearmolecularstructurediffusedoutofthefilmsmorequicklythanthosewithlargerandmorebranchedmolecularstructure.HSPweredevelopedintheprocess,however.HSPhavebeenusedwidelysince1967toaccomplishcorrelationsandtomakesystematiccomparisonswhichonewouldnothavethoughtpossibleearlier.Theeffectsofhydrogenbonding,forexample,areaccountedforquantitatively.Manyofthesecorrelationsarediscussedlater,includingpolymersolubility,swelling,andpermeation;surfacewettinganddewetting;solubilityofinorganicsalts;andbiologicalapplicationsincludingwood,cholesterol,etc.Theexperimentallimitsonthisseeminglyuniversalabilitytopredictmolecularaffinitiesareapparentlygovernedbythelimitsrepresentedbyenergiesoftheliquidtestsolventsthemselves.Therehad/hastobeamoresatisfactoryexplanationofthisuniversalitythanjust“semiempirical”correlations.Idecidedtotrytocollectmyexperienceforthepurposeofareferencebook,bothformyselfandforothers.Atthesametime,asearchofthemajortheoriesofpolymersolutionthermodynamicswasundertakentoexplorehowtheapproachescompared.Akeyelementinthiswastoexplainwhythecorrelationsallseemedtofitwithanapparently“universal”4（or0.25dependingonwhichreferenceisused）.ThisisdescribedinmoredetailinChapter2（Equation2.5andEquation2.6）.Mypresentviewisthatthe“4”istheresultofthevalidityofthegeometricmeanruletodescribenotonlydispersioninteractionsbutalsopermanentdipolepermanentdipoleandhydrogenbonding（electroninterchange）interactionsinmixturesofunlikemolecules.TheHildebrandapproachusesthisandwasthebasisofmyearliestapproach.ThePrigoginecorrespondingstatestheoryyieldsthe“4”intheappropriatemannerwhenthegeometricmeanruleisadopted（Chapter2,Equation2.11）.Anyotherkindofaveraginggivesthewrongresult.Consideringthesefactsandthemassiveamountofdatathathasbeencorrelatedusingthe“4”inthefollowing,itappearsprovenbeyondareasonabledoubtthatthegeometricmeanassumptionisvalidnotonlyfordispersion-typeinteractions（orperhapsmorecorrectlyinthepresentcontextthoseinteractionstypicalofaliphatichydrocarbons）butalsoforpermanentdipolepermanentdipoleandhydrogenbondingaswell.ForthosewhowishtotrytounderstandthePrigoginetheory,IrecommendstartingwithanarticlebyDonaldPatterson.1Thisarticleexplainsthecorrespondingstates/freevolumetheoryofPrigogineandcoworkersinamuchsimplerformthanintheoriginalsource.Patterson2hasalsoreviewedinunderstandablelanguagetheprogressionofdevelopmentsinpolymersolutionthermo-dynamicsfromtheFloryHugginstheory,throughthatofPrigogineandcoworkers,totheso-called“NewFloryTheory.”3Pattersonalsohasbeensokindastoaidmeintherepresentationsoftheearliertheoriesastheyarepresentedhere（especiallyChapter2）.Alloftheprevioustheoriesandtheirextensionsalsocanbefoundinamorerecentbook.4Forthisreason,thesemoreclassical7248_C000.fmPageviiThursday,May24,20071:

40PMtheoriesarenottreatedextensivelyassuchinthisbook.Thestrikingaspectaboutallofthispreviousworkisthatnoonehasdaredtoenterintothetopicofhydrogenbonding.Thepresentquantitativetreatmentofpermanentdipolepermanentdipoleinteractionsandhydrogenbondingiscentraltotheresultsreportedineverychapterinthisbook.AnattempttorelatethisbacktotheprevioustheoriesisgivenbrieflyhereandmoreextensivelyinChapter2.ThisattempthasbeendirectedthroughPatterson,1whichmaybecalledthePrigoginePattersonapproach,ratherthanthroughtheFlorytheory,astherelationswiththeformeraremoreobvious.Istronglyrecommendthatstudiesbeundertakentoconfirmtheusefulnessofthe“structuralparameters”inthePrigoginetheory（ortheFlorytheory）.Itisrecognizedthattheeffectsofsolventmolecularsize,segmentsize,andpolymermolecularsize（andshapes）arenotfullyaccountedforatthepresenttime.Thereishopethatthiscanbedonewithstructuralparameters.Thematerialpresentedherecorrespondstomyknowledgeandexperienceatthetimeofwriting,withallduerespecttoconfidentialityagreements,etc.Iamgreatlyindebtedtomanycolleaguesandsupporterswhohaveunderstoodthatattimesonecanbesopreoccupiedandlostindeepthoughtthatthepresentjustseemsnottoexist.CharlesM.HansenOctober19,1998REFERENCES1.Patterson,D.,RoleofFreeVolumeChangesinPolymerSolutionThermodynamics,J.Polym.Sci.PartC,16,33793389,1968.2.Patterson,D.,FreeVolumeandPolymerSolubility.AQualitativeView,Macromolecules,2（6）,672677,1969.3.Flory,P.J.,ThermodynamicsofPolymerSolutions,DiscussionsoftheFaradaySociety,49,729,1970.4.Lipatov,Y.S.andNesterov,A.E.,PolymerThermodynamicsLibrary,Vol.1,ThermodynamicsofPolymerBlends,TechnomicPublishingCo.,Inc.,Lancaster,PA,1997.7248_C000.fmPageviiiThursday,May24,20071:

40PMPrefacetotheSecondEditionWhenthequestionaboutasecondeditionofthishandbookwasposed,Iwasnotindoubtthatseveraladditionalauthorswerenecessarytomeetthedemandsitwouldrequire.Thewritingsofthefivecontributorsthatwerechosenspeakforthemselves.ThereistheoreticalimpactinChapter3（CostasPanayiotou）andinChapter4（GeorgiosM.Kontogeorgis）.Chapter3introducesstatisticalthermodynamicstoconfirmthedivisionofcohesiveenergyintothreepartsenablingsepara