Solubility Parameters - Theory and Application

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SolubilityParameters:TheoryandApplication
TheAmericanInstituteforConservation
JohnBurke
Solventsareubiquitous:wedependonthemwhenweapplypastesandcoatings,removestainsoroldadhesives,and
consolidateflakingmedia.Thesolubilitybehaviorofanunknownsubstanceoftengivesusacluetoitsidentification,andthe
changeinsolubilityofaknownmaterialcanprovideessentialinformationaboutitsageingcharacteristics.
Ourchoiceofsolventinaparticularsituationinvolvesmanyfactors,includingevaporationrate,solutionviscosity,or
environmentalandhealthconcerns,andoftentheeffectivenessofasolventdependsonitsabilitytoadequatelydissolve
onematerialwhileleavingothermaterialsunaffected.Theselectionofsolventsorsolventblendstosatisfysuchcriterionis
afineart,basedonexperience,trialanderror,andintuitionguidedbysuchrulesofthumbas"likedissolveslike"and
variousdefinitionsofsolvent"strength".Whileseatofthepantsmethodsaresuitableinmanysituations,anydependence
onexperientialreasoningattheexpenseofscientificmethodhaspracticallimitations.Althoughitmaynotbenecessaryto
understandquantummechanicstoremovemaskingtape,anorganizedsystemisoftenneededthatcanfacilitatethe
accuratepredictionofcomplexsolubilitybehavior.
SolubilityScales
Productliteratureandtechnicalreportspresentabewilderingassortmentofsuchsystems:KaouriButanolnumber,
solubilitygrade,aromaticcharacter,analinecloudpoint,waxnumber,heptanenumber,andHildebrandsolubilityparameter,
amongothers.Inaddition,theHildebrandsolubilityparameter,perhapsthemostwidelyapplicableofallthesystems,
includessuchvariationsastheHildebrandnumber,hydrogenbondingvalue,Hansenparameter,andfractionalparameter,to
nameafew.Sometimesonlynumericalvaluesforthesetermsareencountered,whileatothertimesvaluesarepresentedin
theformoftwoorthreedimensionalgraphs,andatriangulargraphcalledaTeasgraphhasfoundincreasingusebecauseof
itsaccuracyandclarity.
Understandably,allthiscanbeslightlyconfusingtotheuninitiated.Graphicplotsofsolventpolymerinteractionsallowthe
fairlyprecisepredictionofsolubilitybehavior,enablingthecontrolofnumerouspropertiesinpracticalapplicationsthatwould
beverydifficultwithoutsuchanorganizingsystem.Yettheunderlyingtheoriesareoftenextremelycomplex,andan
understandingofthe"why"ofaparticularsystemcanbeverydifficult,enoughtodiscouragetheuseofsuchsystems.Many
ofthesystemsmentioned,however,areactuallyquitesimple(thisisespeciallytrueoftheTeasgraph)andcanbeusedto
advantagewithlittleunderstandingofthechemicalprinciplesatwork.
Thispaperwillattempttobridgethesetworealitiesbybrieflyintroducingsolubilitytheoryaswellasitsapplicationsothat
theconservatorwillbebothbetterabletounderstandandprofitablyapplytheconceptsinvolved.Thediscussionwillcenter
onHildebrandsolubilityparametersand,afterlayingatheoreticalfoundation,willconcentrateongraphicplotsofsolubility
behavior.Itshouldberememberedthatthesesystemsrelatetononionicliquidinteractionsthatareextendedtopolymer
interactionswaterbasedsystemsandthosesystemsinvolvingacidbasereactionscannotbeevaluatedbysimplesolubility
parametersystemsalone.
SolutionsandMolecules
Asolvent,usuallythoughtofasaliquid,isasubstancethatiscapableofdissolvingothersubstancesandforminga
uniformmixturecalledasolution.Thesubstancedissolvediscalledthesoluteandisusuallyconsideredtobethe
http://cool.conservationus.org/coolaic/sg/bpg/annual/v03/bp0304.html
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componentpresentinthesmallestamount.Accordingtothisdefinition,analmostdryorslightlyswollenresinfilm
comprisesasolutionofaliquid(thesolute)inaresin(thesolvent),eventhoughconventionallytheliquidisusuallyreferred
toasthesolvent,andtheresinasthesolute.
MolecularAttractions
Liquids(andsolids)differfromgasesinthatthemoleculesoftheliquid(orsolid)areheldtogetherbyacertainamountof
intermolecularstickiness.Forasolutiontooccur,thesolventmoleculesmustovercomethisintermolecularstickinessinthe
soluteandfindtheirwaybetweenandaroundthesolutemolecules.Atthesametime,thesolventmoleculesthemselves
mustbeseparatedfromeachotherbythemoleculesofthesolute.Thisisaccomplishedbestwhentheattractionsbetween
themoleculesofbothcomponentsaresimilar.Iftheattractionsaresufficientlydifferent,thestronglyattractedmoleculeswill
clingtogether,excludingtheweaklyattractedmolecules,andimmiscibility(notabletobemixed)willresult.Oilandwater
donotmixbecausethewatermolecules,stronglyattractedtoeachother,willnotallowtheweakly,attractedoilmolecules
betweenthem.
VanderWaalsForces
ThesestickyforcesbetweenmoleculesarecalledvanderWaalsforces(afterJohannesvanderWaalswhofirst
describedthemin1873).Originallythoughttobesmallgravitationalattractions,VanderWaalsforcesareactuallydueto
electromagneticinteractionsbetweenmolecules.
Theoutershellofaneutralatomormoleculeiscomposedentirelyofnegativelychargedelectrons,completelyenclosing
thepositivelychargednucleuswithin.Deviationsintheelectronshelldensity,however,willresultinaminutemagnetic
imbalance,sothatthemoleculeasawholebecomesasmallmagnet,ordipole.Theseelectrondensitydeviationsdepend
onthephysicalarchitectureofthemolecule:certainmoleculargeometrieswillbestronglypolar,whileotherconfigurations
willresultinonlyaweakpolarity.Thesedifferencesinpolarityaredirectlyresponsibleforthedifferentdegreesof
intermolecularstickinessfromonesubstancetoanother.Substancesthathavesimilarpolaritieswillbesolubleineachother
butincreasingdeviationsinpolaritywillmakesolubilityincreasinglydifficult.
VanderWealsforces,then,aretheresultofintermolecularpolarities.Asweshallsee,accuratepredictionsofsolubility
behaviorwilldependnotonlyondeterminingtheresultofintermolecularattractionsbetweenmolecules,butindiscriminating
betweendifferenttypesofpolaritiesaswell.Asinglemolecule,becauseofitsstructure,mayexhibitvanderWaalsforces
thataretheadditiveresultoftwoorthreedifferentkindsofpolarcontributions.Substanceswilldissolveineachothernot
onlyiftheirintermolecularforcesaresimilar,butparticularlyiftheircompositeforcesaremadeupinthesameway.(Such
typesofcomponentinteractionsincludehydrogenbonds,inductionandorientationeffects,anddispersionforces,whichwill
bediscussedlater.)
TheHildebrandSolubilityParameter
ItisthetotalvanderWaalsforce,however,whichisreflectedinthesimplestsolubilityvalue:theHildebrandsolubility
parameter.Thesolubilityparameterisanumericalvaluethatindicatestherelativesolvencybehaviorofaspecificsolvent.
Itisderivedfromthecohesiveenergydensityofthesolvent,whichinturnisderivedfromtheheatofvaporization.What
thismeanswillbeclarifiedwhenweunderstandtherelationshipbetweenvaporization,vanderWaalsforces,andsolubility.
Vaporization
Whenaliquidisheatedtoitsboilingpoint,energy(intheformofheat)isaddedtotheliquid,resultinginanincreaseinthe
temperatureoftheliquid.Oncetheliquidreachesitsboilingpoint,however,thefurtheradditionofheatdoesnotcausea
furtherincreaseintemperature.Theenergythatisaddedisentirelyusedtoseparatethemoleculesoftheliquidandboil
themawayintoagas.Onlywhentheliquidhasbeencompletelyvaporizedwillthetemperatureofthesystemagainbeginto
rise.Ifwemeasuretheamountofenergy(incalories)thatwasaddedfromtheonsetofboilingtothepointwhenalltheliquid
hasboiledaway,wewillhaveadirectindicationoftheamountofenergyrequiredtoseparatetheliquidintoagas,andthus
theamountofvanderWaalsforcesthatheldthemoleculesoftheliquidtogether.
Itisimportanttonotethatwearenotinterestedherewiththetemperatureatwhichtheliquidbeginstoboil,butthe
amountofheatthathastobeaddedtoseparatethemolecules.Aliquidwithalowboilingpointmayrequireconsiderable
energytovaporize,whilealiquidwithahigherboilingpointmayvaporizequitereadily,orviseversa.Whatisimportantis
theenergyrequiredtovaporizetheliquid,calledtheheatofvaporization.(Regardlessofthetemperatureatwhichboiling
begins,theliquidthatvaporizesreadilyhaslessintermolecularstickinessthantheliquidthatrequiresconsiderableaddition
ofheattovaporize.)
CohesiveEnergyDensity
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Fromtheheatofvaporization,incaloriespercubiccentimeterofliquid,wecanderivethecohesiveenergydensity(c)by
thefollowingexpression
where:
c=Cohesiveenergydensity
h=Heatofvaporization
r=Gasconstant
t=Temperature
Vm=Molarvolume
Inotherwords,thecohesiveenergydensityofaliquidisanumericalvaluethatindicatestheenergyofvaporizationin
caloriespercubiccentimeter,andisadirectreflectionofthedegreeofvanderWaalsforcesholdingthemoleculesofthe
liquidtogether.
Interestingly,thiscorrelationbetweenvaporizationandvanderWaalsforcesalsotranslatesintoacorrelationbetween
vaporizationandsolubilitybehavior.Thisisbecausethesameintermolecularattractiveforceshavetobeovercometo
vaporizealiquidastodissolveit.Thiscanbeunderstoodbyconsideringwhathappenswhentwoliquidsaremixed:the
moleculesofeachliquidarephysicallyseparatedbythemoleculesoftheotherliquid,similartotheseparationsthathappen
duringvaporization.ThesameintermolecularvanderWaalsforcesmustbeovercomeinbothcases.
Sincethesolubilityoftwomaterialsisonlypossiblewhentheirintermolecularattractiveforcesaresimilar,onemightalso
expectthatmaterialswithsimilarcohesiveenergydensityvalueswouldbemiscible.Thisisinfactwhathappens.
SolubilityParameter
In1936JoelH.Hildebrand(wholaidthefoundationforsolubilitytheoryinhisclassicworkonthesolubilityof
nonelectrolytesin1916)proposedthesquarerootofthecohesiveenergydensityasanumericalvalueindicatingthe
solvencybehaviorofaspecificsolvent.
Itwasnotuntilthethirdeditionofhisbookin1950thattheterm"solubilityparameter"wasproposedforthisvalueand
thequantityrepresentedbythesymbol.Subsequentauthorshaveproposedthatthetermhildebrandsbeadoptedfor
solubilityparameterunits,inordertorecognizethetremendouscontributionthatDr.Hildebrandhasmadetosolubilitytheory.
UnitsofMeasurement
Table1listsseveralsolventsinorderofincreasingHildebrandparameter.Valuesareshowninboththecommonform
whichisderivedfromcohesiveenergydensitiesincalories/cc,andanewerformwhich,conformingtostandardinternational
units(SIunits),isderivedfromcohesivepressures.TheSIunitforexpressingpressureisthepascal,andSIHildebrand
solubilityparametersareexpressedinmegapascals(1megapascalormpa=Imillionpascals).Conveniently,SIparameters
areabouttwicethevalueofstandardparameters:
TableI.HildebrandSolubility
Parameters
StandardHildebrandvaluesfrom
Hansen.JournalofPaintTechnology
Vol.39,No.505,Feb1967
SlHildebrandvaluesfromBarton.
HandbookofSolubilityParameters,
CRCPress,1983
ValuesinparenthesisfromCrowley.et
al.,JournalofPaintTechnologyVol.38,
No.496.May1966
solvent
nPentane
(SI)
(7.0)
14.4
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nHexane
7.24
14.9
FreonTF
7.25
nHeptane
(7.4)
15.3
Diethylether
7.62
15.4
1,1,1Trichloroethane
8.57
15.8
nDodecane
16.0
Whitespirit
16.1
Turpentine
16.6
Cyclohexane
8.18
16.8
Amylacetate
(8.5)
17.1
Carbontetrachloride
8.65
18.0
Xylene
8.85
18.2
Ethylacetate
9.10
18.2
Toluene
8.91
18.3
Tetrahydrofuran
9.52
18.5
Benzene
9.15
18.7
Chloroform
9.21
18.7
Trichloroethylene
9.28
18.7
Cellosolveacetate
9.60
19.1
Methylethylketone
9.27
19.3
Acetone
9.77
19.7
Diacetonealcohol
10.18
20.0
Ethylenedichloride
9.76
20.2
Methylenechloride
9.93
20.2
ButylCellosolve
10.24
20.2
Pyridine
10.61
21.7
Cellosolve
11.88
21.9
Morpholine
10.52
22.1
Dimethylformamide
12.14
24.7
nPropylalcohol
11.97
24.9
Ethylalcohol
12.92
26.2
12.93
26.4
Dimethylsulphoxide
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Dimethylsulphoxide
12.93
26.4
nButylalcohol
11.30
28.7
Methylalcohol
14.28
29.7
Propyleneglycol
14.80
30.7
Ethyleneglycol
16.30
34.9
Glycerol
21.10
36.2
Water
23.5
48.0
/calcm3/2=
0.48888x/MPa1/2
(3)
/MPa=
2.0455x/calcm3/2
(4)
Literaturepublishedpriorto1984shouldcontainonlythecommonform,designated,anditishopedthatwherethe
newerSIunitsareused,theyaredesignatedassuch,namely/MPaor(SI).Obviously,onemustbecarefultodetermine
whichsystemofmeasurementisbeingused,sincebothformsarecalledHildebrandparameters.Thispaperwillprimarily
usetheSIvalues,andtheuseofstandardvalueswillbenoted.
SolventSpectrum
InlookingoverTable1,itisreadilyapparentthatbyrankingsolventsaccordingtosolubilityparameterasolvent
"spectrum"isobtained,withsolventsoccupyingpositionsinproximitytoothersolventsofcomparable"strength".If,for
example,acetonedissolvesaparticularmaterial,thenonemightexpectthematerialtobesolubleinneighboringsolvents,
likediacetonealcoholormethylethylketone,sincethesesolventshavesimilarinternalenergies.Itmaynotbepossibleto
achievesolutionsinsolventsfurtherfromacetoneonthechart,suchasethylalcoholorcyclohexaneliquidswithinternal
energiesverydifferentfromacetone.Theoretically,therewillbeacontiguousgroupofsolventsthatwilldissolveaparticular
material,whiletherestofthesolventsinthespectrumwillnot.Somematerialswilldissolveinalargerangeofsolvents,
whileothermightbesolubleinonlyafew.Amaterialthatcannotbedissolvedatall,suchasacrosslinkedthree
dimensionalpolymer,wouldexhibitswellingbehaviorinpreciselythesameway.
SolventMixtures
ItisaninterestingaspectoftheHildebrandsolventspectrumthattheHildebrandvalueofasolventmixturecanbe
determinedbyaveragingtheHildebrandvaluesoftheindividualsolventsbyvolume.Forexample,amixtureoftwoparts
tolueneandonepartacetonewillhaveaHildebrandvalueof18.7(18.3x2/3+19.7x1/3),aboutthesameaschloroform.
Theoretically,sucha2:1toluene/acetonemixtureshouldhavesolubilitybehaviorsimilartochloroform.If,forexample,a
resinwassolubleinone,itwouldprobablybesolubleintheother.Whatisattractiveaboutthissystemisthatitattemptsto
predictthepropertiesofamixtureaprioriusingonlythepropertiesofitscomponents(giventhesolubilityparametersofthe
polymerandtheliquids)noinformationonthemixtureisrequired.
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Fig.ISwellingofLinseedOilFilminSolventsArrangedAccordingtoSolubilityParameter(adaptedfromFeller,Stolow,
andJones,OnPictureVarnishesandTheirSolvents)
PolymerCohesionParameters
Figure1plotstheswellingbehaviorofadriedlinseedoilfilminvarioussolventsarrangedaccordingtoHildebrandnumber.
Ofthesolventslisted,chloroformswellsthefilmtothegreatestdegree,aboutsixtimesasmuchasethylenedichloride,and
overtentimesasmuchastoluene.SolventswithgreaterdifferencesinHildebrandvaluehavelessswellingeffect,andthe
rangeofpeakswellingoccupieslessthantwohildebrandunits.Byextension,wewouldexpectanysolventorsolvent
mixturewithaHildebrandvaluebetween19and20toseverelyswellalinseedoilfilm.(Thecarefulobserverwillnotice
certaininconsistenciesinFig.1whichwillbediscussedlater.)
Sinceapolymerwould.decomposebeforeitsheatofvaporizationcouldbemeasured,swellingbehaviorisoneofthe
waysthatHildebrandvaluesareassignedtopolymers(thegeneraltermcohesionparameterisoftenpreferredtotheterm
solubilityparameterwhenreferringtononliquidmaterials).Anothermethodinvolvescloudpointdeterminationsinwhicha
resinisdissolvedinatruesolventandtitratedwithanothersolventuntilthemixturebecomescloudy,thusidentifyingthe
rangeofsolubility.Testingcloudpointswithavarietyofsolventsanddiluentsenableaprecisedeterminationofcohesion
parametervaluesforpolymers.Othermethodsincludeacombinationofempiricaltests,suchascloudpointand
solubility/swellingtests,withtheadditionoftheoreticalcalculationsbasedoncomparingchemicalstructuretoother
materialsofknownHildebrandvalue.
OtherPracticalSolubilityScales
Similarempiricalmethodshavebeenusedtodevelopothersolubilityscales,unrelatedtotheHildebrandparameter,that
quantifysolventbehavior.Manyoftheseothersystemshavebeendevelopedforparticularapplicationsandareappropriate
foruseinthoseapplicationsbut,althoughagreementbetweenunrelatedsystemsissomewhatloose,itispossibleto
correlatemostoftheseothersystemstotheHildebrandparameter.Whilesuchcorrelationsarenotalwayspracticable,it
doessupporttheHildebrandtheoryasaunifyingapproach,andallowsthetranslationofsolubilityinformationintowhatever
systemisbestfortheapplicationathand.
KauriButanolValue
AparticularlycommoncloudpointtestforrankinghydrocarbonsolventstrengthistheKauriButanoltest.Thekauri
butanolvalue(KB)ofasolventrepresentsthemaximumamountofthatsolventthatcanbeaddedtoastocksolutionof
kauriresin(afossilcopal)inbutylalcoholwithoutcausingcloudiness.Sincekauriresinisreadilysolubleinbutylalcoholbut
notinhydrocarbonsolvents,theresinsolutionwilltolerateonlyacertainamountofdilution."Stronger"solventssuchas
toluenecanbeaddedinagreateramount(andthushaveahigherKBvalue)than"weaker"solventslikehexane.
Fig.2RelationshipBetweenKauriButanolNumberandHildebrandParameter
Figure2illustratesanalmostdirectrelationshipbetweenKBvaluesandHildebrandvalues.Thisrelationshipislinearfor
solventswithKBvaluesgreaterthan35andcanbeexpressed:
/MPa=0.04KB+14.2(5)
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ForaliphatichydrocarbonswithKBvalueslessthan35,therelationship,whilealsolinear,involvescalculationsthat
includecorrectionsformolecularsize.
SolubilityGrade
WhiletheKauriButanoltestmeasurestherelativestrengthofasolvent,anothercloudpointtest,developedbythe
NationalGalleryofArtResearchProject,isusedtodeterminetheSolubilityGradeofapolymer.Inthistest,10%mixtures
ofthepolymerinndodecane(analiphatichydrocarbon,boilingpoint213C)aredilutedwithvaryingpercentagesoftoluene.
TheSolubilityGradeofthepolymeristheminimumpercentoftolueneneededtogiveaclearsolution,thusindicatingthe
strengthofthesolventneededtodissolvethepolymer.Thehigherthepercentageoftolueneintheblend,the"stronger"is
thesolventstrengthoftheblendtheSolubilityGradeisthereforethemildestblendthatcanbeusedtodissolvethepolymer.
Table2givestheSolubilityGradesofseveralpolymers,alongwiththecorrespondingHildebrandnumber(SI)ofthetoluene
dodecanesolution.
Table2.SolubilityGrades(%Toluene)ofPolymersat10%
solidswithHildebrandValuesoftheCorrespondingToluene
Dodecaneblends
Polymer
SolubilityGrade
/MPa
Polyvinylacetate
89
18.05
Polymethylmethacrylate
87
18.00
AcryloidB72(RohmandHaas)
80
17.84
Polynbutylmethacrylate
25
16.58
Polyisobutylmethacrylate
23
16.53
AcryloidB67(RohmandHaas)
18
16.41
ResinAW2
44
16.05
AlthoughtheSolubilityGradegivesusaconvenientlybroadscaleforjudgingthesolubilityofpolymersinmildsolvents,
theHildebrandvalueprovidesaslightadditionaladvantage:theabilitytoassessthesolubilityofthepolymerinsolvent
blendsotherthantoluenedodecane.Todothis,theratioiscalculatedoftherelativecontributionsofthetwonewsolventsin
termsoftheirdistance(inHildebrandunits)fromtheHildebrandvalueofthepolymerSolubilityGrade.Inthiswaywemight
determinethatpolyisobutylmethacrylateshouldformclearsolutionsaboveI0%solidsinasolventofheptanecontainingat
least42%xylene(16.5315.3)+(18.215.3).Whiletheprinciplehereissound,itshouldbenotedthatthefinedivisions
betweenHildebrandvaluesinthisinstancecanonlygiveapproximateresults.
OtherSolubilityScales
Otherempiricalsolubilityscalesincludetheanilinecloudpoint(anilineisverysolubleinaromatichydrocarbons,butonly
slightlysolubleinaliphatics),theheptanenumber(howmuchheptanecanbeaddedtoasolvent/resinsolution),thewax
number(howmuchofasolventcanbeaddedtoabenzene/beeswaxsolution),andmanyothers.Thearomaticcharacterof
asolventisthepercentofthemolecule,determinedbyaddinguptheatomicweights,thatisbenzenestructured(benzeneis
thesimplesthexagonalaromatichydrocarbon).Benzenethereforehas100%aromaticcharacter,toluene85%,anddiethyl
benzene56%aromaticcharacter.Bylooseextension,thearomaticcharacterofamixedsolvent,suchasV.M.andP.
naphthaormineralspirits,isthepercentofaromaticsolventintheotherwisealiphaticmixture.
Thesediversesolubilityscalesareusefulbecausetheygiveconciseinformationabouttherelativestrengthsofsolvents
andallowustomoreeasilydeterminewhatsolventsorsolventblendscanbeusedtodissolveaparticularmaterial.
BecausemostoftheseothersystemscanbemoreorlessdirectlyrelatedtotheHildebrandsolubilityparameter,and
becausetheHildebrandsolventspectrumencompassesthecompleterangeofsolvents,itistheHildebrandsolubility
parameterthatismostfrequentlyencounteredincontemporarytechnicalliterature.
ComponentPolarities
Aswasmentionedabove,thereareinconsistenciesinFig.1thataredifficulttoexplainintermsofsinglecomponent
Hildebrandparameters.Thegraphshowschloroformandethylenedichloride(withHildebrandvaluesof18.7and20.2
respectively)swellingalinseedoilfilmconsiderablymorethanmethylethylketone(MEK)andacetone.Andyetthe
HildebrandvaluesforMEKandacetoneare19.3and19.7,bothbetweenthevaluesforthetwohighswellingsolvents.
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Theoretically,liquidswithsimilarcohesiveenergydensitiesshouldhavesimilarsolubilitycharacteristics,andyetthe
observedbehaviorinthisinstancedoesnotbearthisout.Thereasonforthisisthedifferencesinkindsofpolarcontributions
thatgiverisetothetotalcohesiveenergydensitiesineachcase.
ItwasmentionedthatvanderWaalsforcesresultfromtheadditiveeffectsofseveraldifferenttypesofcomponent
polarities.TheinconsistenciesinFig.1areduetothefactthat,whilethesumtotalcohesiveenergydensitiesaresimilarin
thefoursolventsinquestion,theaddendsthatmakeupthoseindividualtotalsaredifferent.Theseslightdisparitiesinpolar
contributionsresultinconsiderabledifferencesinsolubilitybehavior.Ifthesecomponentdifferencesaretakenintoaccount,
quantified,andincludedinsolubilitytheory,thepredictionofsolubilitybehaviorcanbecomemoreaccurate.Todothis,
differenttypesofpolarcontributionsmustbeexamined,anddifferentiated.
Thefollowingsectionisanintroductiontothethreetypesofpolarinteractionsthataremostcommonlyusedinsolubility
theories:dispersionforces,polarforces,andhydrogenbondingforces.Insomesystems,theHildebrandparameteris
usedinconjunctionwithonlyoneortwooftheseforces(i.e.Hildebrandvalueandhydrogenbondingvalue),whilemore
recentdevelopmentssubdividetheHildebrandparameterintoallthreeforces,orderivativesofthem.Theconcepts
discussedprovideanexcellentfoundationforunderstandingtheinnerworkingsofthepracticalsystemsintroducedlater.It
shouldbestressed,however,thatitispossibletousethesepracticalsystemswithoutathoroughunderstandingofthe
moleculardynamicsonwhichtheyarebased.
DipolesandDipoleMoments
Strongelectromagneticforcesarepresentineveryatomandmolecule.Atthecenterofamoleculeisapositivelycharged
atomicnucleus,whiletheoutersurfaceiscoveredbyadispersedcloudofnegativelychargedelectrons.Thesepositiveand
negativechargesbalanceout,andthemoleculeasawholeisneutral.If,forreasonswewillinvestigate,thedistributionof
theelectroncloudisuneven(maybethickerinoneplaceandthinnerinanother),smalllocalchargeimbalancesarecreated:
thepartsofthemoleculewithagreaterelectrondensitywillbenegativelycharged,andtheelectrondeficientpartswillbe
positivelycharged.Themoleculeasawhole,whilestillneutral,willhavethepropertiesofasmallmagnet,withequalbut
oppositepoles,calleddipoles.
Asinglemolecule,becauseofitsstructure,canhaveseveraldipolesatonce,somestrongandsomeweak,somewhich
cancelout,andsomewhichreinforceeachother.Theresultingsumofallthedipolesiswhatisknownasthedipole
momentofthemolecule.Moleculesthathavepermanentdipolemomentsaresaidtobepolar,whilemoleculesinwhichall
thedipolescancelout(zerodipolemoment)aresaidtobenonpolar.
Thismolecularpolarityisattheheartofintermolecularattractions(imagineapileofsmallmagnetsstickingtogether).The
strengthwithwhichthemoleculesclingtogether,andthereforethecohesiveenergydensityandthesolubilityparameter,is
directlyrelatedtothestrengthofthemoleculardipoles.Butsincetheoverallpolarityofamoleculeisoftenthecombined
resultofseveralcontributingpolarstructures,itisnotenoughtoknowthedipolemomentofamolecule.Thecomponent
polaritiesmustbeconsideredaswell.Moleculesliketobewithothermoleculesoftheirownelectromagnetickind,bothin
termsofpolarstrengthandintermsofpolarcomposition.
DispersionForces
Nonpolarliquids,suchasthealiphatichydrocarbons,haveweakintermolecularattractionsbutnodipolemoment.
Magnetswithoutpoleshowcanthisbe?Thesourceoftheirelectromagneticinteractionscanbedescribedbyquantum
mechanics,andisafunctionoftherandommovementoftheelectroncloudsurroundingeverymolecule.Frominstantto
instant,randomchangesinelectronclouddistributioncausepolarfluctuationsthatshiftaboutthemolecularsurface.
Althoughnopermanentpolarconfigurationisformed,numeroustemporarydipolesarecreatedconstantly,moveabout,and
disappear.
Whentwomoleculesareinproximity,therandompolaritiesineachmoleculetendtoinducecorrespondingpolaritiesin
oneanother,causingthemoleculestofluctuatetogether.Thisallowstheelectronsofonemoleculetobetemporarily
attractedtothenucleusoftheother,andviseversa,resultinginaplayofattractionsbetweenthemolecules.Theseinduced
attractionsarecalledLondondispersionforces,orinduceddipoleinduceddipoleforces.
Thedegreeof"polarity"thatthesetemporarydipolesconferonamoleculeisrelatedtosurfacearea:thelargerthe
molecule,thegreaterthenumberoftemporarydipoles,andthegreatertheintermolecularattractions.Moleculeswithstraight
chainshavemoresurfacearea,andthusgreaterdispersionforces,thanbranchedchainmoleculesofthesamemolecular
weight.ThisdependenceonsurfaceareaexplainswhyconversionsbetweenKauriButanolnumbersandHildebrandvalues
forparaffinmustincludecalculationsformolecularsize.Theintermolecularforcesbetweenparaffinmoleculesareentirely
duetodispersionforces,andarethereforesizedependent.
PolarForces
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Dispersionforcesarepresenttosomedegreeinallmolecules,butinpolarmoleculestherearealsostrongerforcesat
work.Someatomicelementsattractelectronsmorevigorouslythanothers,andpermanentdipolesarecreatedwhen
electronsareunequallysharedbetweentheindividualatomsinamolecule.Ifthemoleculeissymmetrical,thesedipoles
maycancelout.If,ontheotherhand,theelectrondensityispermanentlyimbalanced,withsomeatomsinthemolecule
harboringagreatershareofthenegativechargedistribution,themoleculeitselfwillbepolar.Thepolarityofamoleculeis
relatedtoitsatomiccomposition,itsgeometry,anditssize.Waterandalcoholarestronglypolarmolecules,tolueneisonly
slightlypolar,andtheparaffinhydrocarbonssuchashexaneandStoddardsolventareconsideredtobenonpolar(again,the
attractionsbetweennonpolarmoleculesaredueentirelytodispersionforces).
Polarmoleculestendtoarrangethemselvesheadtotail,positivetonegative,andtheseorientationsleadtofurther
increasesinintermolecularattraction.Thesedipoledipoleforces,calledKeesominteractions,aresymmetricalattractions
thatdependonthesamepropertiesineachmolecule.BecauseKeesominteractionsarerelatedtomoleculararrangements,
theyaretemperaturedependent.HighertemperaturescauseincreasedmolecularmotionandthusadecreaseinKeesom
interactions.
Ontheotherhand,anymolecule,evenifnonpolar,willbetemporarilypolarizedinthevicinityofapolarmolecule,andthe
inducedandpermanentdipoleswillbemutuallyattracted.Thesedipoleinduceddipoleforces,calledDebyeinteractions,are
notastemperaturedependantasKeesominteractionsbecausetheinduceddipoleisfreetoshiftandrotatearoundthe
nonpolarmoleculeasthemoleculesmove.BothDebyeinductioneffectsandKeesomorientationeffectsareconsidered
similarintermsofsolubilitybehaviorandarecollectivelyreferredtoaspolarinteractionsorsimplypolarities.
HydrogenBonding
Aparticularlystrongtypeofpolarinteractionoccursinmoleculeswhereahydrogenatomisattachedtoanextremely
electronhungryatomsuchasoxygen,nitrogen,orfluorine.Insuchcases,thehydrogen'ssoleelectronisdrawntowardthe
electronegativeatom,leavingthestronglychargedhydrogennucleusexposed.Inthisstatetheexposedpositivenucleus
canexertaconsiderableattractiononelectronsinothermolecules,formingaprotonicbridgethatissubstantiallystronger
thanmostothertypesofdipoleinteractions.ThistypeofpolarityissostrongcomparedtoothervanderWaalsinteractions,
thatitisgivenitsownname:hydrogenbonding.Understandably,hydrogenbondingplaysasignificantroleinsolubility
behavior.
TheinconsistenciesinFig.1stemfromadifferenceinhydrogenbondingbetweenthechlorinatedsolventsandthe
ketones.Theintermolecularforcesinlinseedoilareprimarilyduetodispersionforces,withpracticallynohydrogenbonding
involved.Thesepolarconfigurationsareperfectlymatchedbytheintermolecularforcesbetweenchloroformmolecules,thus
encouraginginterpenetrationandswellingofthelinseedoilpolymer.Acetoneandmethylethylketone,however,aremore
polarmolecules,withmoderatehydrogenbondingcapabilities.Eventhoughthetotalcohesiveenergydensityissimilarinall
foursolvents,thedifferencesincomponentforces,primarilyhydrogenbonding,leadtotheobserveddifferences.Acetone
andMEKwouldmuchratherbeattractedtoeachotherthantolinseedoil.
TwoComponentParameters
AschemetoovercometheinconsistenciescausedbyhydrogenbondingwasproposedbyHarryBurrellin1955.This
simplesolutiondividesthesolventspectrumintothreeseparatelists:oneforsolventswithpoorhydrogenbondingcapability,
oneforsolventswithmoderatehydrogenbondingcapability,andathirdforsolventswithstronghydrogenbondingcapability,
ontheassumptionthatsolubilityisgreatestbetweenmaterialswithsimilarpolarities.Thissystemofclassificationisquite
successfulinpredictingsolventbehavior,andisstillwidelyusedinpracticalapplications.Theclassificationaccordingto
Burrellmaybebrieflysummarizedasfollows:
Weakhydrogenbondingliquids:hydrocarbons,chlorinatedhydrocarbons,andnitrohydrocarbons.
Moderatehydrogenbondingliquids:ketones,esters,ethers,andglycolmonoethers
Stronghydrogenbondingliquids:alcohols,amines,acids,amides,andaldehydes
Latersystemsassignspecificvaluestohydrogenbondingcapacity,andplotthosevaluesagainstHildebrandvaluesona
twodimensionalgraph.AlthoughhydrogenbondingvaluesaregenerallydeterminedusingIRspectroscopy(bymeasuring
thefrequencyshiftaparticularsolventcausesindeuteratedmethanol),anotherinterestingmethodusesthespeedofsound
throughpaperthathasbeenwetwiththesolventbeingtested.Sincepaperfibersareheldtogetherlargelybyhydrogen
bonds,thepresenceofaliquidcapableofhydrogenbondingwilldisruptthefiberfiberbondsinpreferencetofiberliquid
bonds.Thisdisruptionofpaperfiberbondingwilldecreasethevelocityofsoundtravellingthroughthesheet.Water,capable
ofahighdegreeofhydrogenbonding,isusedasareferencestandard,andthehydrogenbondingvalueofaliquidistheratio
ofitssonicdisruptionrelativetowater.Inthistest,alkaneshavenoeffectonfiberhydrogenbonding,givingthesamesonic
velocitiesasairdriedpaper.
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HydrogenbondingisatypeofelectrondonoracceptorinteractionandcanbedescribedintermsofLewisacidbase
reactions.Forthisreasonothersystemshaveattemptedtheclassificationofsolventsaccordingtotheirelectrondonatingor
acceptingcapability.SuchextensionsoftheHildebrandparametertoincludeaciditybasicityscales,andultimatelyionic
systems,arerelativelyrecentandoutsidethescopeofthispaper.
ThreeComponentParameters
SolubilitybehaviorcanbeadequatelydescribedusingHildebrandvalues,althoughinsomecasesdifferencesinpolar
compositiongiveunexpectedresults(Fig.1,forexample).PredictionsbecomemoreconsistentiftheHildebrandvalueis
combinedwithapolarvalue(i.e.hydrogenbondingnumber),givingtwoparametersforeachliquid.Evengreateraccuracyis
possibleifallthreepolarforces(hydrogenbonding,polarforces,anddispersionforces)areconsideredatthesametime.
Thisapproachassignsthreevaluestoeachliquidandpredictsmiscibilityifallthreevaluesaresimilar.
Aslongasdataispresentedintheformofasinglelist,orevenatwodimensionalgraph,itcanbeeasilyunderstoodand
applied.Withtheadditionofathirdterm,however,problemsariseinrepresentingandusingtheinformationthemanipulation
ofthreeseparatevaluespresentscertaininconveniencesinpracticalapplication.Itisforthisreasonthatthedevelopment
andtheuseofthreecomponentparametersystemshascenteredonsolubilitymapsandmodels.
3DModels
Whilepolymersolubilitiesmaybeeasilypresentedasaconnectedgroupofsolventsonalist,orasaspecificareaona
graph,thedescriptionofsolubilitiesinthreedimensionsisunderstandablymoredifficult.Mostresearchershavetherefore
reliedonthreedimensionalconstructionswithinwhichallthreecomponentparameterscouldberepresentedatonce.
In1966,Crowley,Teague,andLoweofEastmanChemicaldevelopedthefirstthreecomponentsystemusingthe
Hildebrandparameter,ahydrogenbondingnumber,andthedipolemomentasthethreecomponents.Ascalerepresenting
eachofthesethreevaluesisassignedtoaseparateedgeofalargeemptycube.Inthisway,anypointwithinthecube
representstheintersectionofthreespecificvalues.Asmallball,supportedonarod,isplacedattheintersectionofvalues
foreachindividualsolvent(Figure3).
Fig.3.Athreedimensionalboxusedtoplotsolubilityinformation(afterCrowley,TeagueandLowe)a=Hildebrandvalue,
p=dipolemoment,h=hydrogenbondingvalue
Onceallthesolventpositionshavebeenlocatedwithinthecubeinthisway,solubilitytestsareperformedonindividual
polymers.Thepositionofsolventsthatdissolveapolymerareindicatedbyablackball,nonsolventsbyawhiteone,and
partialsolubilitiesareindicatedbyagreyball.Inthiswayasolidvolume(orthreedimensionalarea)ofsolubilityisformed,
withliquidswithinthevolumebeingactivesolvents(blackballs),andliquidsoutsidethevolumebeingnonsolvents(white
balls).Aroundthesurfaceofthevolume,attheinterfacebetweentheareaofsolubilityandthesurroundingnonsolventarea,
theballsaregrey.
Oncethevolumeofsolubilityforapolymerisestablished,itbecomesnecessarytotranslatethatinformationintoaform
thatispractical.Thismeanstransformingthe3Dmodel(difficulttocarryaround)intoa2Dgraph(easiertopublish).Thisis
usuallydoneinoneoftwosimilarways.Inbothcases,thedataisplottedonarectangulargraphthatrepresentsonlytwoof
thethreecomponentparameterscales(onesideofthecube).
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Fig.4.ApproximateRepresentationsofSolidModelandSolubilityMapforCelluloseAcetate(fromCrowley,atal,Journal
ofPaintTechnologyVol39,504,Jan1967)graphthatrepresentseitherasingleslicethroughthevolumeataspecifiedvalue
onthethirdcomponentparameterscale,oratopographicmapthatindicatsseveralvaluesofthethirdparameteratthesame
time(seeFigure4).Becausethevolumeofsolubilityforapolymerusuallyhasanunusualshape,severalgraphsareoften
neededforanindividualpolymerifitstotalsolubilitybehavioristobeshown.
Mapssuchasthesecan'beusedinconjunctionwithatableofthreecomponentparametersforindividualsolvents,andin
thiswayprovideuseableinformationaboutsolventpolymerinteractionsandallowtheformulationofpolymerorsolvent
blendstosuitspecificapplications.Datapresentedinthiswayisnotonlyconcise,butsavesconsiderabletimebyallowing
thepredictionofsolubilitybehaviorwithoutrecoursetoextensiveempiricaltesting.!tisforthesereasonsthatsolubility
mapsareoftenincludedintechnicalreportsandmanufacturer'sproductdatasheets.Howgraphsareactuallyusedto
accomplishthesepurposeswillbedescribedlaterintermsofthetriangularTeasgraph,inwhichtheseproceduresare
similarbutgreatlysimplified.
HansenParameters
ThemostwidelyacceptedthreecomponentsystemtodateisthethreeparametersystemdevelopedbyCharlesM.
Hansenin1966.HansenparametersdividethetotalHildebrandvalueintothreeparts:adispersionforcecomponent,a
hydrogenbondingcomponent,endapolarcomponent.ThisapproachdiffersfromCrowley'sintwomajorways:first,by
usingadispersionforcecomponentinsteadoftheHildebrandvalueasthethirdparameter,andsecond,byrelatingthe
valuesofallthreecomponentstothetotalHildebrandvalue.ThismeansthatHansenparametersareadditive:
t2= d2+ p2+ h2(6)
where
t2=
TotalHildebrandparameter
d2=
dispersioncomponent
p2=
polarcomponent
h2=
hydrogenbondingcomponent
Thenumericalvaluesforthecomponentparametersaredeterminedinthefollowingway:First,thedispersionforcefora
particularliquidiscalculatedusingwhatiscalledthehomomorphmethod.Thehomomorphofapolarmoleculeisthe
nonpolarmoleculemostcloselyresemblingitinsizeandstructure(nbutaneisthehomomorphofnbutylalcohol).The
Hildebrandvalueforthenonpolarhomomorph(beingdueentirelytodispersionforces)isassignedtothepolarmoleculeas
itsdispersioncomponentvalue.Thisdispersionvalue(squared)isthensubtractedfromtheHildebrandvalue(squared)of
theliquid,theremainderdesignatedasavaluerepresentingthetotalpolarinteractionofthemolecule a(nottobeconfused
withthepolarcomponent p).Throughtrialanderrorexperimentationonnumeroussolventsandpolymers,Hansen
separatedthepolarvalueintopolarandhydrogenbondingcomponentparametersbestreflectingempiricalevidence.Table3
listsHansenparametersforseveralsolvents.
Table3,HansenParametersforSolventsat25C
(valuesselectedfromHansen's1971parameterslistedin
HandbookofSolubilityParameters,AllanF.M.Barton.Ph.D.,
CRCPress,1983,page153157)
/MPa
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/MPa
Solvent
t
nButane
14.1
14.1
0.0
0.0
nPentane
14.5
14.5
0.0
0.0
nHexane
14.9
14.9
0.0
0.0
nHeptane
15.3
15.3
0.0
0.0
nOctane
15.5
15.5
0.0
0.0
Isooctane
14.3
14.3
0.0
0.0
nDodecane
16.0
16.0
0.0
0.0
Cyclohexane
16.8
16.8
0.0
0.2
Methylcyclohexane
16.0
16.0
0.0
0.0
Benzene
18.6
18.4
0.0
2.0
Toluene
18.2
18.0
1.4
2.0
Napthalene
20.3
19.2
2.0
5.9
Styrene
19.0
18.6
1.0
4.1
oXylene
18.0
17.8
1.0
3.1
Ethylbenzene
17.8
17.8
0.6
1.4
pDiethylbenzene
18.0
18.0
0.0
0.6
Chloromethane
17.0
15.3
6.1
3.9
Methylenechloride
20.3
18.2
6.3
6.1
1,1Dichloroethylene
18.8
17.0
6.8
4.5
Ethylenedichloride
20.9
19.0
7.4
4.1
Chloroform
19.0
17.8
3.1
5.7
1,1Dichloroethane
18.5
16.6
8.2
0.4
Trichloroethylene
19.0
18.0
3.1
5.3
Carbontetrachloride
17.8
17.8
0.0
0.6
Chlorobenzene
19.6
19.0
4.3
2.0
oDichlorobenzene
20.5
19.2
6.3
3.3
1,1,2Trichlorotrifluoroethane
14.7
14.7
1.6
0.0
Alkanes
AromaticHydrocarbons
Halohydrocarbons
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Ethers
Tetrahydrofuran
19.4
16.8
5.7
8.0
1,4Dioxane
20.5
19.0
1.8
7.4
Diethylether
15.8
14.5
2.9
5.1
Dibenzylether
19.3
17.4
3.7
7.4
Acetone
20.0
15.5
10.4
7.0
Methylethylketone
19.0
16.0
9.0
5.1
Cyclohexanone
19.6
17.8
6.3
5.1
Diethylketone
18.1
15.8
7.6
4.7
Acetophenone
21.8
19.6
8.6
3.7
Methylisobutylketone
17.0
15.3
6.1
4.1
Methylisoamylketone
17.4
16.0
5.7
4.1
Isophorone
19.9
16.6
8.2
7.4
Di(isobutyl)ketone
16.9
16.0
3.7
4.1
Ethylenecarbonate
29.6
19.4
21.7
5.1
Methylacetate
18.7
15.5
7.2
7.6
Ethylformate
18.7
15.5
7.2
7.6
Propylene1,2carbonate
27.3
20.0
18.0
4.1
Ethylacetate
18.1
15.8
5.3
7.2
Diethylcarbonate
17.9
16.6
3.1
6.1
Diethylsulfate
22.8
15.8
14.7
7.2
nButylacetate
17.4
15.8
3.7
6.3
Isobutylacetate
16.8
15.1
3.7
6.3
2Ethoxyethylacetate
20.0
16.0
4.7
10.6
Isoamylacetate
17.1
15.3
3.1
7.0
Isobutylisobutyrate
16.5
15.1
2.9
5.9
Nitromethane
25.1
15.8
18.8
5.1
Nitroethane
22.7
16.0
15.5
4.5
2Nitropropane
20.6
16.2
12.1
4.1
Ketones
Esters
NitrogenCompounds
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2Nitropropane
20.6
16.2
12.1
4.1
Nitrobenzene
22.2
20.0
8.6
4.1
Ethanolamine
31.5
17.2
15.6
21.3
Ethylenediemme
25.3
16.6
8.8
17.0
Pyridine
21.8
19.0
8.8
5.9
Morpholine
21.5
18.8
4.9
9.2
Analine
22.6
19.4
5.1
10
NMethyl2pyrrolidone
22.9
18.0
12.3
7.2
Cyclohexylamine
18.9
17.4
3.1
6.6
Quinoline
22.0
19.4
7.0
7.6
Formamide
36.6
17.2
26.2
19.0
N,NDimethylformamide
24.8
17.4
13.7
11.3
Carbondisulfide
20.5
20.5
0.0
0.6
Dimethylsulphoxide
26.7
18.4
16.4
10.2
Ethanethiol
18.6
15.8
6.6
7.2
Methanol
29.6
15.1
12.3
22.3
Ethanol
26.5
15.8
8.8
19.4
Allylalcohol
25.7
16.2
10.8
16.8
1Propanol
24.5
16.0
6.8
17.4
2Propanol
23.5
15.8
6.1
16.4
1Butanol
23.1
16.0
5.7
15.8
2Butanol
22.2
15.8
5.7
14.5
Isobutanol
22.7
15.1
5.7
16.0
Benzylalcohol
23.8
18.4
6.3
13.7
Cyclohexanol
22.4
17.4
4.1
13.5
Diacetonealcohol
20.8
15.8
8.2
10.8
Ethyleneglycolmonoethylether
23.5
16.2
9.2
14.3
Diethyleneglycolmonomethylether
22.0
16.2
7.8
12.7
Diethyleneglycolmonoethylether
22.3
16.2
9.2
12.3
Ethyleneglycolmonobutylether
20.8
16.0
5.1
12.3
SulfurCompounds
Alcohols
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Diethyleneglycolmonobutylether
20.4
16.0
7.0
10.6
1Decanol
20.4
17.6
2.7
10.0
Formicacid
24.9
14.3
11.9
16.6
Aceticacid
21.4
14.5
8.0
13.5
Benzoicacid
21.8
18.2
7.0
9.8
Oleicacid
15.6
14.3
3.1
14.3
Stearicacid
17.6
16.4
3.3
5.5
Phenols
Phenol
24.1
18.0
5.9
14.9
Resorcinol
29.0
18.0
8.4
21.1
mCresol
22.7
18.0
5.1
12.9
Methylsalicylate
21.7
16.0
8.0
12.3
Ethyleneglycol
32.9
17.0
11.0
26.0
Glycerol
36.1
17.4
12.1
29.3
Propyleneglycol
30.2
16.8
9.4
23.3
Diethyleneglycol
29.9
16.2
14.7
20.5
Triethyleneglycol
27.5
16.0
12.5
18.6
Dipropyleneglycol
31.7
16.0
20.3
18.4
Water
47.8
15.6
16.0
42.3
Acids
PolyhydricAlcohols
HansenModel
CharlesHansenalsousedathreedimensionalmodel(similartothatusedbyCrowleyetal.)toplotpolymersolubilities.
Hefoundthat,bydoublingthedispersionparameteraxis,anapproximatelysphericalvolumeofsolubilitywouldbeformed
foreach.polymer.Thisvolume,beingspherical,canbedescribedinasimpleway(Figure5):thecoordinatesatthecenterof
thesolubilityspherearelocatedbymeansofthreecomponentparameters( d, p, h),andtheradiusofthesphereis
indicated,calledtheinteractionradius(R).Table4givestheHansenparametersandinteractionradiusofseveral
polymers.
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Fig.5,TheHansenvolumeofsolubilityforapolymerislocatedwithina3Dmodelbygivingthecoordinatesofthecenter
ofasolubilitysphere( d, p, h)anditsradiusofinteraction(R).Liquidswhoseparametersliewithinthevolumeareactive
solventsforthatpolymer.
Table4.HansenParametersandInteractionRadiusofPolymers
(from:Solubilityinthecoatingsindustry,C.M.Hansen,Sksnd.Tidskr.Faerg.Lack,17,
69.1971)
Polymer(tradename,supplier)
/MPa1/2
d
Celluloseacetate(CellicloreA,Bayer)
18.6
12.7
11.0
7.6
Chlorinatedpolypropylene(ParlonP10,Hercules)
20.3
6.3
5.4
10.6
Epoxy(Epikote1001,Shell)
20.4
12.0
11.5
12.7
Isopreneelastomer(CeriflexIR305,Shell)
16.6
1.4
0.8
9.6
Cellulosenitrate(1/2sec,H23,Hforn)
15.4
14.7
8.8
11.5
Polyamide,thermoplastic(Versamid930,GeneralMills)
17.4
1.9
14.9
9.6
Poly(isobutylene)LutonalIC123,BASF)
14.5
2.5
4.7
12.7
Poly(ethylmethacrylate)(Lucite2042,DuPont)
17.6
9.7
4.0
10.6
Poly(methylmethacrylate)(RohmandHaas)
18.6
10.5
7.5
8.6
Polystyrene(PolystyreneLO,BASF)
21.3
5.8
4.3
12.7
Poly(vinylacetate)(Mowilith50,Hoechst)
20.9
11.3
9.6
13.7
Poly(vinylbutyral)(ButvarB76,Shawnigan)
18.6
4.4
13.0
10.6
Poly(vinylchloride)(VilpaKR,k=50,Montecatini)
18.2
7.5
8.3
3.5
Saturatedpolyester(Desmophen850,Bayer)
21.5
14.9
12.3
16.8
Apolymerisprobablysolubleinasolvent(orsolventblend)iftheHansenparametersforthesolventliewithinthe
solubilitysphereforthepolymer.Inordertodeterminethis(withoutbuildingamodel)itmustbecalculatedwhetherthe
distanceofthesolventfromthecenterofthepolymersolubilitysphereislessthantheradiusofinteractionforthepolymer:
D(SP)=[4( ds dp)2+( ps pp)2+( hs hp)2](7)
where
D(SP)=Distancebetweensolventandcenterofpolymersolubilitysphere
x s=Hansencomponentparameterforsolvent
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x p=Hansencomponentparameterforpolymer
(Thefigure"4"inthefirsttermofequation(7),whichdoublesthedispersioncomponentscale,isintendedtocreatea
sphericalvolumeofsolubility.)Ifthedistance(D(sp))islessthantheradiusofinteractionforthepolymer,thesolvent
wouldbeexpectedtodissolvethepolymer.Thismethodavoidstherelianceongraphic,plotsofsolubilitybehaviorandcan
beusedeffectivelyinsolelynumericalform.Themathematicsinvolvedareinconvenienthowever(especiallywhensolvent
blendsareconcerned),anditisperhapsforthisreasonthattheuseofthisexcellentsystemisnotmorewidespread.
HansenGraph
Hansenparametersarebothreasonablyaccurateinpredictingsolubilitybehaviorandconciseintheirrepresentationof
thatinformation..Accuratebecauseprecisevaluesforallthreecomponentparametersareutilized,andconcisebecausethe
entiresolubilityvolumeforapolymercanbenumericallyindicatedbyfourterms:onesetofparametersandaradius.
Ontheotherhand,atwodimensionalgraphsacrificessomeofthataccuracyandconcisenessinreturnforasystemthat
clearlyillustratestherelativepositionsofnumerousmaterials,andcanbeeasilyusedinpracticalapplications.Predicting
whetherapolymerissolubleinamixtureoftwosolvents,forexample,whilepossiblemathematically,isaccomplishedona
graphbydrawingalinebetweenthetwosolventsandseeingwhetherthatlinepassesthroughtheareaofsolubilityforthe
polymer.
Figure6.Hansengraphofsolubilityareasforpoly(methylmethacrylate)(MMA)andpoly(ethylmethacrylate)(EMA).Liquid
parametersareindicatedbysymbolssmallcirclesindicatecenterofsolubilityspheres.Liquidsoutsidethesolubilityareaof
apolymerarenonsolvents.ThedottedlineillustratesallthepossiblemixturesofMEKandethanolnoticethatMMAwill
tolerateagreaterproportionofethanolthanwillEMAAccordingly,MMAshouldbesolubleintoluene/acetone3:1,butnotin
100%toluene.
Figure7.Hansengraphofsolubilityareasforpolyvinylacetate)(PVA),poly(vinylbutyral)(PVB),andpoly(vinylchloride).
ThistypeofgraphusesonlytwoofthethreeHansenparameters.
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AswasthecasewithCrowley'ssolubilitymaps,Hansen'sthreedimensionalvolumescanbesimilarlyillustratedintwo
dimensionsbyplottingacrosssectionthroughthecenterofthesolubilitysphereonagraphthatusesonlytwoofthethree
parameters,mostcommonly pand h.Figures6and7illustratethisapproachbyplottingthevolumesofsolubilityforfive
polymers:polyvinylacetate,polyvinylbutyral,polyvinylchloride,polymethylmethacrylate,andpolyethylmethacrylate.The
graphsusethehydrogenbondingcomponentparameterandthepolarcomponentparameterastheXandYaxis,
respectively,andplotthecirclegeneratedbytheradiusofinteractionforeachpolymerthesymbolsindicatetherespective
locationsofsolvents.
Hansengraphsareeasytousebecausesolventpositionsareconstantandpolymersolubilityareasmaybedrawnwitha
compassfurthermore,solventblendingcalculationscanbedonewithapencilandruler.Theaccuracyofpredictingsolubility
behaviorisabout90%,withsolventlocationsnearesttheedgeofasolubilityareabeingtheleastpredictable.Thisisdueto
thethreedimensionalnatureoftheactualsolubilitysphere.Whenreducedtotwodimensions,solventsthatappearnearthe
edgeinsidethesolubilityareamayinfactbeoutsideit,infrontorbehind,inthreedimensions.
FractionalParameters
ThedivisionoftheHildebrandparameterintothreecomponentHansenparameters(dispersionforce,polarforce,and
hydrogenbondingforce)considerablyincreasestheaccuracywithwhichnonionicmolecularinteractionscanbepredicted
anddescribed.Hansenparameterscanbeusedtointerpretnotonlysolubilitybehavior,butalsothemechanicalpropertiesof
polymers,pigmentbinderrelationships,andtheactivityofsurfactantsandemulsifiers.
Beingathreecomponentsystem,however,placeslimitationsontheeasewithwhichthisinformationcanbepractically
applied.Translatingthisthreecomponentdataontoatwodimensionalgraph(byignoringoneofthecomponents)solvesthis
problembutsacrificesacertainamountofaccuracyatthesametime.Whatisnisasimple,planargraphonwhichpolymer
solubilityareascanbedrawnintheirentiretyintwodimensions.Atriangulargraphmeetingthesequalificationswas
introducedbyJeanP.Teasin1968,usingasetoffractionalparametersmathematicallyderivedfromthethreeHansen
parameters.Becauseofitsclarityandeaseofuse,theTeasgraphhasfoundincreasingapplicationamongconservatorsfor
problemsolving,documentation,andanalysis,andisanexcellentvehicleforteachingpracticalsolubilitytheory.
TheTeasGraph
Inordertoplotallthreeparametersonasingleplanargraph,acertaindeparturemustbemadefromestablishedsolubility
theory.TheconstructionoftheTeasgraphisbasedonthehypotheticalassumptionthatallmaterialshavethesame
Hildebrandvalue.Accordingtothisassumption,solubilitybehaviorisdetermined,notbydifferencesintotalHildebrand
value,butbytherelativeamountsofthethreecomponentforces(dispersionforce,polarforce,andhydrogenbonding
force)thatcontributetothetotalHildebrandvalue.Thisallowsustospeakintermsofpercentagesratherthanunrelated
sums.
HansenparametersareadditivecomponentsofthetotalHildebrandvalue(Equation6).Inotherwords,ifallthreeHansen
values(squared)areaddedtogether,thesumwillbeequaltotheHildebrandvalueforthatliquid(squared).Teas
parameters,calledfractionalparameters,aremathematicallyderivedfromHansenvaluesandindicatethepercent
contributionthateachHansenparametercontributestothewholeHildebrandvalue:
Inotherwords,ifallthreefractionalparametersareaddedtogether,thesumwillalwaysbethesame(100).
Forexample,thealkanes,withintermolecularattractionsdueentirelytodispersionforces,arerepresentedbyadispersion
parameterof100,indicatingtotality,withbothpolarandhydrogenbondingparametersofzero.Moleculesthataremorepolar
havedispersionparametersoflessthan100,theremainderproportionatelydividedbetweenpolarandhydrogenbonding
contributionsastheparticularHansenparametersdictate.
BecauseHildebrandvaluesarenotthesameforallliquids,itshouldberememberedthattheTeasgraphisanempirical
systemwithlittletheoreticaljustification.SolventpositionswereoriginallylocatedonthegraphaccordingtoHansenvalues
(usingEquation8),andsubsequentlyadjustedtocorrespondtoexhaustiveempiricaltesting.Thislackoftheoretical
foundation,however,doesnotpreventtheTeasgraphfrombeinganaccurateandusefultool,perhapsthemostconvenient
methodbywhichsolubilityinformationcanbeillustrated.FractionalparametersforsolventsarelistedinTable6,attheend
ofthispaper.
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Figure8.TheTeasgraphisanoverlayofthreesolubilityscales.
TheTriangularGraph
ThelayoutofatriangulargraphisconfusingatfirsttopeoplewhoareaccustomedtothecommonCartesianrectangular
coordinategraph.Insteadoftwoaxesperpendiculartoeachother,therearethreeaxesorientedat60,andinsteadofthese
threeaxesrequiringthreedimensionsinspace,thetriangulargraphisflat.Furthermore,onaartesiangraphallthescales
graduateoutfromthesameorigin,butonatriangulargraphthezeropointofanyonescaleistheupperlimitofanotherone.
Thisunusualconstructionderivesfromtheoverlayofthreeidenticalscales,eachproceedinginadifferentdirection(Figure
8).Inthisway,anypointwithinthetriangulargraphusesthreecoordinates,thesumofwhichwillalwaysbethesame:100
(Figure9).
Figure9.Atanypointonatriangulargraph,allthreecoordinatesaddupto100.
SolventLocations
Bymeansofatriangulargraph,solventsmaybepositionedrelativetoeachotherinthreedirections(Figure10).Alkanes,
whoseonlyintermolecularbondingisduetodispersionforces,arelocatedinthefarlowerrightcorneroftheTeasgraph,the
cornerthatcorrespondsto100%dispersionforcecontribution,and0%contributionfrompolarorhydrogenbondingforces.
Movingtowardthelowerleftcorner,correspondingto100%hydrogenbondingcontribution,thesolventsexhibitincreasing
hydrogenbondingcapability,culminatingatthealcoholsandwater,moleculeswithrelativelylittledispersionforcecompared
totheirverygreathydrogenbondingcontribution.Movingfromthebottomofthegraphupwardsweencountersolventsof
increasingpolarity,duelesstohydrogenbondingfunctionalgroupsthantoanincreasinglygreaterdipolemomentofthe
moleculeasawhole,suchastheketonesandnitrocompounds.
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Figure10.TheTeasGraph
NumbersindicatesolventlocationsandrefertoTable5,pg.4345.
Overall,thesolventsaregroupedclosertothelowerrightapexthantheothers.Thisisbecausethedispersionforceis
presentinallmolecules,polarornot,anddeterminingthedispersioncomponentisthefirstcalculationinassigningHansen
parameters,fromwhichtheTeasfractionalparametersarederived.Unfortunately,thisgreatlyoveremphasizesthe
dispersionforcerelativetopolarforces,especiallyhydrogenbondinginteractions.
SolventClasses
Figure11illustratessolventsonaTeasgraphgroupedaccordingtoclasses.Increasingmolecularweightwithineach
classshiftstherelativepositionofasolventonthegraphclosertothebottomrightapex.Thisisbecause,asmolecular
weightincreases,thepolarpartofthemoleculethatcausesthespecificcharacteridentifyingitwithitsclass,calledthe
functionalgroup,isincreasingly"diluted"byprogressivelylarger,nonpolar"aliphatic"molecularsegments.Thisgivesthe
moleculeasawholerelativelymoredispersionforceandlessofthepolarcharacterspecifictoitsclass.
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Figure11.Solventsgroupedaccordingtoclasses.Withineachclass,increasingmolecularweightshiftsthesolvent
positiontowardtherightaxis,correspondingtoanincreaseindispersioncontributionrelativetopolarcontributions.
Thistrendtowardlesspolaritywithincreasingmolecularweightwithinaclassalsoaccountsfortheobservationthatlower
molecularweightsolventsareoften"stronger"thanhighermolecularweightsolventsofthesameclass,although
determinationsofsolventstrengthmustreallybemadeintermsofthesolventspositionrelativetothesolubilityareaofthe
solute.(Anotherreasonforlowmolecularweightsolventsseemingmoreactiveisthatsmallermoleculescandisperse
throughoutsolidmaterialsmorerapidlythantheirbulkierrelatives.)
Theonlyclassinwhichincreasingmolecularweightplacesthesolventfurtherawayfromthelowerrightcorneristhe
alkanes.Aspreviouslystated,theintermolecularattractionsbetweenalkanesaredueentirelytodispersionforces,and
accordingly,Hansenparametervaluesforalkanesshowzeropolarcontributionandzerohydrogenbondingcontribution.
SincefractionalparametersarederivedfromHansenparameters,onewouldexpectallthealkanestobeplacedtogetherat
theextremerightapex.
Observedbehaviorindicates,however,thatdifferentalkanesdohavedifferentsolubilitycharacteristics,perhapsbecause
ofthetendencyoflargerdispersionforcestomimicslightlypolarinteractions.Forthisreason,Teasadjustedthelocationsof
thealkanestocorrespondtoempiricalevidence,usingKauriButanolvaluestoassignalkanelocationsonthegraph.Several
othersolventlocationswerealsoshiftedslightlytoproperlyreflectobservedsolubilitycharacteristics.
Thepositionofwateronthechartisveryuncertain,duetotheioniccharacterofthewatermolecule,andtheplacementin
thispaperisaccordingtorecentpublishedvalues(Teas,1976).Thepresenceofwaterinasolventblend,however,canalter
dramaticallytheaccuracyofsolubilitypredictions.
[Itshouldbenotedthatthepositionofmethylenechlorideisalsocorrectaccordingtorecentvalues.Manyearlier
publicationshavegivenmethylenechlorideincorrectparametersproperlycorrespondingtoHansen'svaluesformethyl
chloride,adifferentchemical,possiblyduetocalculationerror.]
PolymerSolubilityWindows
Giventhesolventpositions,itispossibletoindicatepolymersolubilitiesusingmethodssimilartothoseusedbyCrowley
andHansen:apolymeristestedinvarioussolvents,andtheresultsindicatedonthegraph(a3Dmodelisnolonger
necessary).Atfirst,individualliquidsfromdiverselocationsonthegrapharemixedwiththepolymerunderinvestigation,
andthedegreeofswellingordissolutionnoted.Liquidsthatareactivesolvents,forexample,mighthavetheirpositionson
thegraphmarkedwithareddot.Marginalsolventsmightbemarkedwithayellowdot,andnonsolventsmarkedwithblack.
Oncethisisdone,asolidareaontheTeasgraphwillcontainallthereddots,surroundedwithyellowdots(seeFigure12).
Theedgesofthisarea,orpolymersolubilitywindow,canbemorecloselydeterminedinthefollowingway.Twoliquids
neartheedgeofthesolubilitywindowarechosen,onewithinthewindow(reddot),andoneoutsidethewindow(blackdot).
Dissolution(orswelling)ofthepolymeristhentestedinvariousmixturesofthesetwoliquids,usingcloudpoint
determinationsifaccuracyisessential,andthemixturejustproducingsolubilityisnotedonthegraph,thusdeterminingthe
edgeofthesolubilitywindow.(Themixturewouldbelocatedonalinebetweenthetwoliquids,atapointcorrespondingin
distancetotheratiooftheliquidsinthemixture.)Ifthisprocedureisrepeatedinseverallocationsaroundtheedgeofthe
solubilitywindow,theboundariescanbeaccuratelydetermined.Interestingly,somecompositematerials(suchas
rubber/resinpressuresensitiveadhesives,orwaxresinmixtures)canexhibittwoormoreseparatesolubilitywindows,more
orlessoverlapping,thatreflectthedegreeofcompatibilityandtheconcentrationoftheoriginalcomponents.
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Figure12.Thesolubilitywindowofahypotheticalpolymer(circlesindicatesolvents).
Thismethodofsolubilitywindowdeterminationcanbeperformedonsamplesunderamicroscope,andtheresultsplotted
onaTeasgraph.Incaseswherethesolubilitiesofartifactualmaterialsaretobeapriortotreatment,itisoftenunnecessary
todelineatetheentiresolubilitywindowofthematerialsinquestion.Itcansufficetorecordthereactionofthematerialsto
theprogressivemixturesofafewselectedsolventsunderworkingconditionsinordertodetermineappropriateworking
solutions.
Temperature,concentration,viscosity
Thesolubilitywindowofapolymerhasaspecificsize,shape,andplacementontheTeasgraphdependingonthepolarity
andmolecularweightofthepolymer,andthetemperatureandconcentrationatwhichthemeasurementsaremade.Most
publishedsolubilitydataarederivedfrom10%concentrationsatroomtemperature.
Heathastheeffectofincreasingthesizeofthesolubilitywindow,duetoanincreaseinthedisorder(entropy)ofthe
system.Themoredisorderedasystemis(increasedentropy),thelessitmattershowdissimilarthesolubilityparametersof
thecomponentsare.Sinceentropyalsorelatestothenumberofelementsinasystem(moreelements=moredisorder),
polymergradesoflowermolecularweight(manysmallmolecules)willhavelargersolubilitywindowsthanpolymergradesof
highermolecularweight(fewerlargemolecules).
Concentrationalsohasaneffectonsolubility.Asstated,mostpolymersolubilitywindowsaredeterminedat10%
concentrationofpolymerinsolvent.Becauseanincreaseinpolymerconcentrationcausesanincreaseintheentropyofthe
system(moreelements=moredisorder),solubilityinformationcanbeconsideredaccurateforsolutionsofhigher
concentrationaswell.Solventevaporationasapolymerfilmdriesservestoincreasethepolymerconcentrationinthe
solvent,thusinsuringthatthetwomaterialsstaymixed.Itispossible,however,forpolymersolutionsoflessthan10%to
phaseseparate(becomeimmiscible),duetoadecreaseinentropy.Thisisparticularlysusceptibletopolymersolvent
combinationsattheedgeofthepolymersolubilitywindow.Inotherwords,withlowerpolymerconcentrationthereisan
increaseintheorderofthesystem(lessentropy)therefore,thesizeofthesolubilitywindowbecomessmaller(thereisless
differencetoleratedbetweensolventandpolymersolubilityvalues).
Solutionviscosityalsovariesdependingonwhereinthepolymersolubilitywindowthesolventislocated.Onemight
expectviscositytobeataminimumwhenasolventnearthecenterofapolymersolubilitywindowisused.However,thisis
notthecase.Solventsatthecenterofapolymersolubilitywindowdissolvethepolymersoeffectivelythattheindividual
polymermoleculesarefreetouncoilandstretchout.Inthisconditionmolecularsurfaceareaisincreased,witha
correspondingincreaseinintermolecularattractions.Themoleculesthustendtoattractandtangleoneachother,resultingin
solutionsofslightlyhigherthannormalviscosity.
Whendissolvedinsolventsslightlyoffcenterinthesolubilitywindow,polymermoleculesstaycoiledandgrouped
togetherintomicroscopicclumpswhichtendtoslideoveroneanother,resultinginsolutionsoflowerviscosity.Assolvents
nearerandnearertheedgeofthesolubilitywindowareusedtodissolvethepolymer,however,theseclumpsbecome
progressivelylargerandmoreconnectedandviscosityagainincreasesuntilultimatelypolymerliquidphaseseparation
occurrsastheregionofthesolubilitywindowboundaryiscrossed.
Driedfilmproperties
Thepositionofasolventinthesolubilitywindowofapolymerhasamarkedeffectonthepropertiesofnotonlythe
polymersolventsolution,butonthedriedfilmcharacteristicsofthepolymeraswell.Becauseoftheuncoilingofthepolymer
molecule,films(whetheradhesivesorcoatings)castfromsolventsolutionsnearthecenterofthesolubilitywindowexhibit
greateradhesiontocompatiblesubstrates.Thisisduetotheincreaseinpolymersurfaceareathatcomesincontactwith
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thesubstrate.(Hildebrandparameterscanberelatedtosurfacetension,andadhesionisgreatestwhenthepolaritiesof
adhesiveandadherendaresimilar.)
Manyotherpropertiesofdriedfilms,suchasplasticcrazingorgaspermeabilityarerelatedtotherelativepositionthatthe
originalsolventoccupiedinthesolubilitywindowofthepolymer.Thedegreeofbothcrazingandpermeabilityispredictably
lesswhensolventsmorecentraltothesolubilitywindowhavebeenused.
Evaporationratesandsolubility
Solventevaporationratescanalsohaveamarkedaffectondriedfilmproperties.Thesolubilityparametersofsolvent
blendscanchangeduringfilmdryingbecauseofthedifferenceinevaporationratesofthecomponentliquids.Ifavolatile
truesolventismixedwithaslowevaporatingnonsolvent,thecompatibilitybetweensolventsandpolymercanshiftasthe
truesolventevaporates.Thepredominanceofthenonsolventduringthelaststagesofdryingcanresultinadiscontinuous,
porousfilmwithhigheropacityanddecreasedresistancetowaterandoxygendeterioration.(Theremaybeinstanceswhere
thesepropertiesaredesirable.)
Thiscanbeavoided,however,byeitherblendingasmallamountofahighboilingtruesolventintothesolventmixture
(thissolventremainstothelastandinsuresmiscibility),orbymakingsurethat,ifanazeotropicmixtureisformedon
evaporation,theparametersoftheazeotropeliewithinthepolymersolubilitywindow.
Anazeotropeisamixtureoftwoormoreliquidsthathasaconstantboilingpointataspecificconcentration.Whentwo
liquidsaremixedthatarecapableofforminganazeotrope,themorevolatileliquidwillevaporatemorequicklyuntilthe
concentrationreachesazeotropicproportions.Atthatpoint,theconcentrationwillremainconstantasevaporationcontinues.
Ifthepositionoftheazeotropicmixturelieswithinthesolubilitywindow,compatibilitywiththepolymerwillcontinue
throughoutthedryingprocess.Thiscanbedeterminedbyconsultingatableofazeotropesandcheckingthelocationofthe
mixtureontheTeasgraphinrelationtothepolymersolubilitywindow.(Methodsofplottingsolventmixturesaredescribedin
thenextsection.)
Blendingsolvents
Teasgraphisparticularlyusefulasanaidtocreatingsolventmixturesforspecificapplications.Solventscaneasilybe
blendedtoexhibitselectivesolubilitybehavior(dissolvingonematerialbutnotanother),ortocontrolsuchpropertiesas
evaporationrate,solutionviscosity,degreeoftoxicityorenvironmentaleffects.TheuseoftheTeasgraphcanreducetrial
anderrorexperimentationtoaminimum,byallowingthesolubilitybehaviorofasolventmixturetobepredictedinadvance.
Becausesolubilitypropertiesarethenetresultofintermolecularattractions,amixturewiththesamesolubilityparameters
asasingleliquidwill,inmanycases,exhibitthesamesolubilitybehavior.Determiningthesolubilitybehaviorofasolvent
mixture,therefore,issimplyamatteroflocatingthesolubilityparametersofthemixtureontheTeasgraph.Therearetwo
waysbywhichthismaybeaccomplished:mathematically,bycalculatingthefractionalparametersofthemixturefromthe
fractionalparametersoftheindividualsolvents,andgeometrically,bysimplydrawingalinebetweenthesolventsand
measuringtheratioofthemixtureonthegraph.Themathematicalmethodisthemostaccurate,andisappropriatefor
mixturesofthreeormoresolvents.Thegeometricalmethodisthemostconvenientandissuitableformixturesoftwo
solvents,orforveryroughguesseswhenthreesolventsareinvolved.
Themathematicalmethod
Thesolubilityparameterofamixtureofliquidsisdeterminedbycalculatingthevolumewisecontributionsofthesolubility
parametersoftheindividualcomponentsofthemixture.Inotherwords,thefractionalparametersforeachliquidare
multipliedbythefractionthattheliquidoccupiesintheblend,andtheresultsforeachparameteraddedtogether.For
example,givenamixtureof20%acetoneand80%toluene:
Inthisway,thepositionofthesolventmixturecanbelocatedontheTeasgraphaccordingtoitsfractionalparameters.
Calculationsformixturesofthreeormoresolventsaremadeinthesameway.
Thegeometricmethod
ThegeometricmethodoflocatingasolventmixtureontheTeasgraphinvolvessimplydrawingalinebetweenthetwo
solventsinthemix,andfindingthepointonthelinethatcorrespondstothevolumefractionsofthemixture.
Acetone:
fd
fd
fh
47(x.20)=9.4
32(x.20)=6.4
21(x.20)=4.2
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Toluene:
80(x.80)=64.0
7(x.80)=5.6
13(x.80)=10.4
fd=73.4
fh=12.0
fp=14.6
20/80Mix:
Figure13.Amixtureof20%acetoneand80%toluenecanbelocatedontheTeasgraphbyusingapencilandruler.The
mixtureliesonalineconnectingthetwoliquids,atadistanceequaltotheratioofthemixture,andclosertotheliquid
presentinthegreatestamount.ThisisillustratedinFigure13forthesame20%acetone,80%toluenemixture.Aline
connectingacetoneandtolueneisdrawnontheTeasgraph.Apointisthenlocatedontheline,20%ofthelengthoftheline
awayfromtoluene.Itisimportanttorememberthatthelocationofamixturewillbeclosertotheliquidpresentinthe
greatestamount.
Solventblendsandsolubilitywindows
WhatisinterestingaboutvisualizingsolventblendsontheTeasgraphisthecontrolwithwhicheffectivesolventmixtures
canbeformulated.Forexample,twoliquidsthatarenonsolventsforaspecificpolymercansometimesbeblendedinsuch
awaythatthemixturewillactasatruesolvent.Thisispossibleifthegraphpositionofthemixtureliesinsidethesolubility
windowofthepolymer,andismosteffectiveifthedistanceofthenonsolventsfromtheedgeofthesolubilitywindowisnot
toogreat.ThisisillustratedinFigure14.
Figure14.Amixture(M)ofnonsolvents(A,B)mayactasatruesolventforapolymerifthemixtureislocatedinsidethe
solubilitywindowforthepolymerontheTeasgraph.
Thisphenomenonisparticularlyvaluablewhenselectivesolventactionisrequired.Oftenitisnecessarytoselectively
dissolveonematerialwhileleavingothermaterialsunaltered,asinthecaseofremovingthevarnishfromapainting,some
adhesivetapefromtheimageareaofaprint,orwhenaconsolidantmustnotdissolvethematerialbeingconsolidated.
Sometimesthesolubilitiesofallthematerialsinvolvedaresosimilarthatselectinganappropriateandsafesolventcanbe
difficult.Insuchcasesitishelpfultoindicatethesolubilitywindowsofboththematerialthatneedstobedissolved(varnish,
adhesive,consolidant),andthematerialsthatmustbeprotected(media),onaTeasgraph.Thiscanbeaccomplishedby
simplesolubilitytesting,notingtheresultsofthetestsonthegraph.
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Figure15.Insituationswhereonematerialmustbedissolved(darkcircle)whileanothermustremainunaffected(shaded
area),itishelpfultoplotthesolubilityofbothmaterialsonthegraph.Asolventblendcanthenbeformulated(triangle)that
selectivelydissolvesonlythepropermaterial(seetext).
Oncethishasbeendone,itiseasytoseetheoverlapofsolubilities,andtheareaswheresolubilitiesaremutually
exclusive,iftheyexist.Asolventblendcanthenbeformulatedthatactivelydissolvesthepropermaterial,whilepositioned
asfarawayfromthesolubilitywindowoftheothermaterialaspossible(Figure15).Itisimportanttorememberthat
differencesinevaporationratescanshiftthesolubilityparameteroftheblendasthesolventsevaporate,andthismustbe
takenintoaccount.Additionally,whileamaterialmaynotshownsignsofsolutioninasolventorsolventblend,thesolvent
maystilladverselyaffectthematerial,forexamplebysofteningthematerialorleachingoutlowmolecularweight
components.Suchchangescanbeirreversibleandmustbeconsideredpriortoembarkingonatreatment.
Solventmixturescales
AlthoughtheTeasgraphisusefulandinformativewhendealingwithcomplexsolubilityquestions,inmostdaytoday
situationschoosingasolventisastraightforwardprocedurethatwouldbeunnecessarilycomplicatedbyhavingtoplotentire
solubilitywindows.Inmostcases,thedegreeofsolubilityofamaterialissimplytestedinvariousconcentrationsoftwoor
threesolvents,inordertodeterminethemildestsolventcapableofformingasolution.
Perhapsthemostoftenusedsolventmixturesareblendsofaliphaticandaromatichydrocarbons,sometimeswiththe
additionofacetone.Thisisbecausethesearchforthemildestsolventisoftensynonymouswiththesearchfortheleast
polarsolvent(andthealiphatichydrocarbonsaretheleastpolarpossible).
Figure16.Somecommonsolventblends(a=acetone,t=toluene,h=heptane,e=ethanol,m=methylenechloride,f=Freon
TF).Inmostcases,dispersionforcevaluesgivearelativeindicationofsolventstrength(100=weakest,30=strongest).
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Testingwhetherapolymerissuitableforuseinconservation,forexample,usuallyinvolvesdeterminingthemildest
solventmixturethatwilldissolvebothagedandunagedsamples.Forthispurpose,variousconcentrationsoftoluenein
cyclohexaneareusedshouldthepolymerproveinsolubleinstraighttoluene,however,increasingamountsofacetonearea
untilsolubilityisachieved.Thistypeofsolubilitytestanticipatesthechoicesthatwillbemadeinworkingsituations.
Lookedatintermsoffractionalparameters,whatisbeingdeterminedinsuchtestsisessentiallythelocationoftheedge
ofthesolubilitywindowforthepolymerinrelationto,thelowerrightcorneroftheTeasgraph.Figure15illustratesvarious
mixturesofheptane,toluene,andacetone.Itcanbeenclearlyseenthatsolventstrengthincreaseswithgreaterdistance
fromthe100%dispersionaxis.Blendsoftrichlorotrifluoroethane(FreonTF)andmethylenechlorideaswellasblendsof
tolueneethanolarealsoillustrated.Inallcases,increasingsolventstrengthfollowsdecreasingdispersionforcecontribution.
Forthisreason,theuseoffractionaldispersionvalues(Table5)isanexcellentmethodforconciselydesignatingrelative
solventstrength,inplaceofothermorelimitedscales(KauriButanolnumber,aromaticcontent,etc.).Thebenefitsofthis
approachincludetheuseofastandarddesignationthatencompassestheentirerangeofsolventstrengths,andtheabilityto
easilyenlargethedesignationtoincludemoreprecisesolubilityparameterdataifnecessary.
Table5.Mixturesofheptane.toluene,andacetone,
withcorrespondingdispersionforcevalues.fd
locationsareillustratedinFigure15
%Heptane
%Toluene
%Acetone
Approx.fd
100
100
75
25
95
50
50
90
25
75
85
100
80
85
15
75
70
30
70
55
45
65
40
60
60
26
76
55
10
90
50
100
47
SolventsandHealth
Aswehaveshown,theTeasgraphcanbeausefulguideintailoringsolventblendstosuitspecificapplications.By
adjustingthepositionoftheblendrelativetothesolubilitywindowofapolymersuchpropertiesassolutionviscosityand
adhesioncanbeoptimized.Evaporationratescanbecontrolledindependentlyofsolventstrength,andtheeffectsof
temperatureandconcentrationcanbeanticipated.
Afurtheradvantagethatcanbederivedfromthislatitudeincreatingsolventmixturesisthepossibilityofchoosing
solutionsbasedondegreeoftoxicity.Asolventmixturehavingagraphpositionclosetoanothersolventwillhavesuch
similarsolubilitycharacteristicstothatsolventthatitcanbeusedinterchangeablyinmanyapplications.Forexample,a
petroleumsolventof30%aromaticcharacterismoreorlessthesamewhetherthearomaticcontentisduetobenzene(very
toxic)ortotoluene(moderatelytoxic).Byextension,amixtureofethanol/toluene50:50mightbeusedinplaceof
tetrahydrofuraninsomeapplications,andtoluenemightbereplacedwitha3:1mixtureofStoddardsolventandacetone.In
suchcases,itshouldbepointedoutthatthesimilaritybetweensolventsandblendshavingthesamenumericalparameters
decreasesasthedistancebetweenthecomponentsoftheblendincreases.Wherealternateblendsareeffective,however,
theuseofalesstoxicreplacementcanbeasensiblechoice,andtheTeasgraphausefultool.
Conclusion
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Thetheoryofsolubilityparametersisaconstantlydevelopingbodyofscientificconceptsthatcanbeofimmensepractical
assistancetotheconservator.Throughthemediaofsolubilitymaps,complexmolecularinteractionscanbevisualizedand
understood,andinthisway,solubilitytheorycansimplyfunctionasaladdertobeleftbehindoncethebasicconceptsare
assimilated.Ontheotherhand,thesolutiontoanunusualproblemcanoftenbeputwithinreachbygraphicallyplotting
solubilitybehavioronaTeasgraph.
Inthenearfuture,theextensionofsolubilitytheorytoencompassionicandwaterbasedsystemsisconceivable,andthe
developmentofsimplecomputerprogramstomanipulatemulticomponentsolubilityparameterdata,alongwithaccessible
databasesofmaterialsolubilities,isprobable.Untilthattime,bothconservatorsandtheobjectsintheirchargecancontinue
toprofitbytheuse,eitherconceptualorreal,ofsolubilityparametertheory.
JohnBurke
TheOaklandMuseumAugust1984
Table6.FractionalSolubilityParameters
(ValuesfromGardonandTeasTreatiseonCoatings,Vol.2,
CharacterizationofCoatings:PhysicalTechniques,PartII,
MeyersandLong,Eds.,MarcelDekker,NY,1976.Valuesin
bracketsderivedfromHansen's1971parametersinHandbookof
SolubilityParameters,A.Barton.CRCPress.1983,using
Equation4)
NumbersinleftcolumnrefertosolventpositionsinTeasgraph,
Figure10,paw30.
solvent
100fd
100fp
Alkanes
100fh
nPentane
100
nHexane
100
nHeptane
100
nDodecane
100
Cyclohexane
94
VM&PNaphtha
94
MineralSpirits
90
AromaticHydrocarbons
5
Benzene
78
14
Toluene
80
13
oXylene
83
12
Naphthalene
70
22
Styrene
78
18
10
Ethylbenzene
87
10
11
pDiethylbenzene
97
HalogenCompounds
12
Methylenechloride
59
21
20
13
Ethylenedichloride
67
19
14
14
Chloroform
67
12
21
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15
Trichloroethylene
68
12
20
16
Carbontetrachloride
85
13
17
1,1,1Trichloroethane
70
19
11
18
Chlorobenzene
65
17
19
Trichlorotrifluoroethane
90
10
Ethers
20
Diethylether
64
13
23
21
Tetrahydrofuran
55
19
26
22
Dioxane
67
26
23
MethylCellosolve
39
22
39
24
Cellosolve8
42
20
38
25
ButylCellosolve
46
18
36
26
MethylCarbitol
44
21
35
27
Carbitol
48
23
29
25
ButylCarbitol
46
18
36
Ketones
28
Acetone
47
32
21
29
Methylethylketone
[53]
[30]
[17]
30
Cyclohexanone
55
28
17
Diethylketone
56
27
17
Mesityloxide
55
24
21
31
Methylisobutylketone
58
22
20
32
Methylisoamylketone
62
20
18
Isophorone
51
25
24
33
Diisobutylketone
[67]
[16]
[17]
Esters
34
Methylacetate
45
36
19
35
Propylenecarbonate
48
38
14
36
Ethylacetate
51
18
31
Trimethylphosphate
[39]
[37]
[24]
Diethylcarbonate
64
12
24
42
39
19
Diethylsulfate
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Diethylsulfate
42
39
19
37
nButylacetate
60
13
27
Isobutylacetate
60
i5
25
38
Isobutylisobutyrate
63
12
25
39
Isoamylacetate
60
12
28
40
Cellosolveacetate
51
i5
34
Ethyllactate
44
21
35
Butyllactate
40
20
32
NitrogenCompounds
41
Acetonitrile
39
45
16
42
Butyronitrile
44
41
15
43
Nitromethane
40
47
13
44
Nitroethane
44
43
13
45
2Nitropropane
50
37
13
46
Nitrobenzene
52
36
12
47
Pyridine
56
26
18
48
Morpnoline
57
15
28
49
Aniline
50
19
31
50
NMethyl2pyrrolidone
48
32
20
Diethylenetriamine
38
30
32
51
Cyclohexylamine
[64]
[12]
[24]
Formamide
28
42
30
52
NNDimethylformamide
41
32
27
SulfurCompounds
88
53
Carbondisulfide
54
Dimethylsulfoxide
41
36
23
Alcohols
55
Methanol
30
22
48
56
Ethanol
36
18
46
57
1Propanol
40
16
44
58
2Propanol
[41]
[16]
[43]
29/32
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59
1Butanol
43
15
42
2Butanol
[44]
[16]
[40]
Benzylalcohol
48
16
36
60
Cyclohexanol
50
12
38
61
namylalcohol
46
13
41
62
Diacetonealcohol
45
24
31
2Ethyl1hexanol
50
41
PolyhydricAlcohols
63
Ethyleneglycol
30
18
52
64
Glycerol
25
23
52
65
Propyleneglycol
34
16
50
66
Diethyleneglycol
31
29
40
67Water
18
28
54
MiscellaneousLiquids
68
Phenol
46
15
39
69
Benzaldehyde
61
23
16
70
Turpentine
77
18
71
Dipentene
75
20
Formicacid
[33]
[28]
[39]
Aceticacid
[401
[22]
[38]
Oleicacid
[62]
[14]
[24]
Stearicacid
[65]
[131
[22]
Linseedoil
66
17
17
Cottonseedoil
67
15
18
Neetsfootoil
69
14
17
Pineoil
70
14
16
Spermoil
75
11
14
Mineraloil
100
References
Barton,AllanF.M.,HandbookofSolubilityParametersendOtherCohesionParametersBocaRaton,Florida:CRCPress,
Inc.,1983.
30/32
10/10/2016
Burrell,Harry,"TheChallengeoftheSolubilityParameterConcept,"JournalofPaintTechnology,Vol.40,No.520,1968.
Crowley,JamesD.,0.S.Teague,Jr.,andJackW.Lowe,Jr.,"AThreeDimensionalApproachtoSolubility,"Journalof
PaintTechnology,Vol.38,No.496,1966.
Durrans,ThomasH.,Solvents.London:ChapmanandHallLtd.,1971.
Feller,RobertL.,NathanStolow,andElizabethH.Jones,OnPictureVarnishesandTheirSolvents.Cleveland:ThePress
ofCaseWesternReserveUniversity,1971.
Feller,RobertL.,"TheRelativeSolventPowerNeededtoRemoveVariousAgedSolventTypeCoatings,"inConservation
andRestorationofPictorialArt,BromelleandSmith,Eds.,London:Butterworths1976
Hildebrand,J.H.,TheSolubilityofNonElectrolytesNewYork:Reinhold,1936
Hansen,CharlesM.,"TheThreeDimensionalSolubilityParameterKeytoPaintComponentAffinities:1.Solvents
Plasticizers,Polymers,andResins,"JournalofPaintTechnology,Vol.39,No.505,1967.
Hansen,CharlesM.,"TheThreeDimensionalSolubilityParameterKeytoPaintComponentAffinities:11.Dyes,
Emulsifiers,MutualSolubilityandCompatibility,andPigments,"JournalofPaintTechnology,Vol.39,No.511,1967.
Hansen,CharlesM.,"TheThreeDimensionalSolubilityParameterKeytoPaintComponentAffinities:111.Independent
CalculationsoftheParameterComponents,"JournalofPaintTechnology,Vol.39,No.511,1967.
Hansen,CharlesM.,"TheUniversalityoftheSolubilityParameterConcept,"I&ECProductResearchand
Development,Vol.8,No.1,1969.
Hedley,terry,"SolubilityParametersandVarnishRemoval:ASurvey,"TheConservator,No.4,1980.
Teas,JeanP.,"OraphicAnalysisofResinSolubilities,"JournalofPaintTechnology,Vol.40,No.516,1968.
Teas,JeanP.,PredictingResinSolubilities.Columbus,Ohio:AshlandChemicalTechnicalBulletin,Number1206.
Torraca,Giorgio,SolubilityandSolventsforConservationProblemsRome:ICCROM,1978.
PublicationHistory
Received:Fall1984
Thispaperwassubmittedindependentlybytheauthor,andwasnotdeliveredattheBookandPaperspecialtygroup
sessionoftheAICAnnualMeeting.Ithasnotreceivedpeerreview
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