6/7/2015

OsmoticBlistersinCoatingsandAdhesivesMetalFinishing

Ourwebsiteusescookies.Cookiesenableustoprovidethebestexperiencepossibleandhelpusunderstandhowcustomersuseourwebsite.
Oursitewon'tworkwithoutthem.Bycontinuingtouseourwebsiteyouacceptouruseofcookies.Findoutmoreaboutcookies

MetalFinishing

Youarehere: Home / Features / OsmoticBlistersinCoatingsandAdhesives

Feature
OsmoticBlistersinCoatingsandAdhesives
12October2011
EdPetrie,EMPSolutions,Cary,N.C.

MetalFinishing'sadhesionandbondingexpertdiscusseshowblisteringcanbe
reducedoreveneliminatedbytheproperselectionofcoatingmaterialsandsubstrate
surfacepreparation.
Osmoticblisteringisoneofthemostcommonfailuremodesforcoatingsinwetserviceenvironments,yetitisnotawellunderstood
failuremechanism.Osmoticblisteringisalltoofamiliarincertainapplications,suchasindustrialmarinecoatingsandliningsandgel
coatsonboatsandswimmingpools.Itcanalsoaffectadhesivebondsofdecorativeplasticshellstospas,hottubs,andother
applicationswheremoistureisprevalent.Osmoticblisteringisalsooftenevidentincoatingsonconcrete.
Heavyorganiccoatingsandlinersarefrequentlythoughttobebarrierstothepassageofmoisture.But,infact,allpolymersare
permeabletomoistureandgases,tosomeextent.Thisseeminglysmalldegreeofmoisturepermeationandthesoluble
contaminantsthatcanbecarriedwiththemoistureisthemaincauseforosmoticblistering.
PERMEATIONANDOSMOSIS
Osmoticblisteringgenerallyrelatestothickpolymericcoatings,thinfilms,orthindecorativelaminatesthatarebondedtoamore
structuralmaterial.Osmoticblisteringisoftenattributedtopoorinterfacialadhesion,butitisnotsomuchanadhesionfailure
mechanismasafailureofthesubstrateorcoating.Theresultcanbedevastatingchickenpoxlikeblistersonasurfacethatis
generallyprizedforhavingafaultlessappearance.
Themechanismthatcausesosmoticblisteringisthesamenomatterwhattheproduct.Osmoticblisteringrequiresthefollowing:(1)
apermeablefilm(2)arelativelyimpermeablesubstrate(3)waterdissolvedsolidsand(4)aconcentrationgradient.The
concentrationgradientisthedrivingforceforthecreationandexpansionofablister.
Perhaps,theeasiestwayofunderstandingosmoticblisteringistoconsideroneofitsmostnotoriousanddestructiveproblems.
Sincethe1980s,blisteringhasbeenespeciallywellrecognizedandunderstoodbythemanufacturersofmarineboathullsand
suppliersofresinsthatgointoaquaticproducts.Thisisduetothenearconstantwatercontactintheseapplications.
Usingaboathullasanexample,theexteriorgelcoatisusuallyapolyestercoatinghavingpropertiesdifferentthanthatoftheglass
reinforcedpolyesterlaminatedbelowit.Thegelcoathaspigmentforcolorandgloss,UVresistance,abrasionresistance,andgood
moistureresistance,asitprovidestheoutsidesurfacethatisnexttothewater.However,thegelcoatdoesnotprovideafinite
barriertothepassageofmoisture.Themechanismcontributingtotheformationofboathullblistershasbeenreportedinthe
technicalliterature.
Insimpleterms,whathappensiswaterpenetratestheoutsidecoatingbothasvaporandasliquidwater.Allpolymersarepermeable
towatertosomedegreeduetotheparticularlysmallsizeoftheH2Omolecule.Therateofpermeabilitywilldependonthenatureof
thepolymer,itsbarriercharacteristics,itsthickness,andtemperature.Oncethewaterhaspenetratedtheoutsidecoating,itthen
passesintothefiberfilledpolyesterlaminatestructureinsimilarfashion.However,oncewithinthelaminatestructure,theglass
fiberspromotethepermeationbyactingascapillarytunnelstotransportthewatermoleculesfurtherintothelaminate.
Thepermeatedwaterwilleither:(1)degrade(hydrolyze)thepolyesterresinataratethatdependsonitsmolecularstructureand/or
(2)gointochemicalsolutionwithwatersolublematerialswithintheresin.Thesewatersolublematerialsincludeproductsinthe
formulationthathavenotfullyreacted.Temperaturewillaccelerateboththepermeationandthedegradation/solubilization
processes.
Tovaryingdegrees,thesewatersolublematerialsarepresentinallcuredpolyesterresins.Theirpresencedoesnotnecessarily
resultinacompositehavinglowblisterresistance.However,iftheyareconcentratedbeyondnormallimits,oriftheyare
concentratedinagivenarea,thenblisteringwillresult.Ontheotherhand,potentialhydrolysisproductsfromaninferiorresininthe
backingcompositecouldprovideaconstantsupplysourceforosmoticpressurebuildup.
Adrivingforceforwatertoenterthebackinglaminateiscausedbythewatersolutionintheresinhavingagreaterconcentrationof
watersolublematerialthanthewaterontheoutsideofthestructure.Oneofthestrongestdrivesinnatureistoreachequilibrium,
andthisiswhathappensinthiscase.Thewaterfromtheoutsideisdrivenintotheareasthathaveagreaterconcentrationof
watersolublematerialstodilutethesolution.Thisiscalledanosmoticforce.Inessence,theflowintothelaminateexceedsthe
flowout,sothatthefluidbuildsandthepressureincreasestoformablister.Withtime,theblistergrowslargerandslowlystarts
separatingthecoatingorouterlayersoflaminatefromthebulklaminatecausingadomedshape.Astimegoeson,theblistermay
breakfromtheinternalpressureandformapinholeorcrackintheexteriorsurface.
Theblisteringofdecorativegelcoatsonotherglassreinforcedresinstructuressuchswimmingpools,bathroomappliances,and
spasareasimilarproblem.Alloftheseproductsutilizeatwopartlaminate:onepartprovidesafunctionalandaestheticappearance
(athinwaterpermeablelayer)whiletheotherpartprovidesstructuralintegrity.Inhottubs,blisteringhasbeennoticedevenwhen
theouterlayerisathinacrylicshellandnotagelcoating.
BLISTERINGOFCOATINGSONMETALSUBSTRATES

http://www.metalfinishing.com/view/21322/osmoticblistersincoatingsandadhesives/

1/2

6/7/2015

OsmoticBlistersinCoatingsandAdhesivesMetalFinishing

Thesameforcesareatworktocreateblistersincoatingsonmetalsubstrates.Paintfilmsaresemipermeablemembranesthatare
permeabletowater,butimpermeabletodissolvedsolids.Thedrivingforcehereisawatersolublematerialateithertheinterfaceor
withintheinterface.Thewatersolublematerialthatcausestheosmoticgradientisgenerallyeitheraninorganicsalt,theproductsof
corrosion,orretainedsolventsinthecoating.
Osmoticblisteringhasbeenrelatedtochlorides,sulfates,andotherinorganicsolublesoftenfoundonsubstrates.Thesematerials
couldresultfromenvironmentalcontaminationorfromdepassivatingsaltssuchaschloridesandsulfates.Waterextractable
materialsaccidentallyordeliberatelyentrainedinthecoatingmayalsocauseproblems.
OsmoticgradientsmayalsoarisefromcorrosionproductssuchasFe(OH)2. Wherechloridesandsulfatesaresimultaneously
present,thecorrosionproductsareevenmoresolubleinwater.WithcertaincoatingbindersthehighpHgeneratedatthecathode
mayhydrolyzethebinderandthiscanbeasourceofsolublesaswell.
Suchblisteringcanalsobeduetohydrophilicsolventsandotherdiluentsbeingentrappedinthecoatingfilm.Iftheseproductsare
misciblewithwater,theycouldbedrawnthroughthefilmosmotically.Agreaterconcentrationthenoccursattheinterfacewhich
needstobecompensatedbyanosmoticpressure,allowingmorewaterthroughthefilmtoreducetheconcentrationattheinterface.
SUMMARY
Blisteringisoneofthemaincausesofthefailureofheavyindustrialcoatingsandofdecorativecoatingsonpolyesterlaminates.
Whenoneseesblistersforming,theimmediatethoughtisgenerallythatthisiseitherduetopoorchemicalresistanceofthecoating
ortopooradhesionattheinterface.However,thedrivingmechanismisthesolubilizationofmaterials,waterdiffusingintothe
coatingstoequilibratetheconcentration,andthenwatercollectingattheinterfacetoinitiateandgrowdelamination.
Blisteringcangenerallybereducedoreliminatedbytheproperselectionofcoatingsmaterialsandsubstratesurfacepreparation.
Effortsalsoneedtobemadetochoosematerialsortoprovideprocessingmethodsthatdonotleavewatersolublecomponents.
Onecanalsochoosecoatingsthataregoodbarrierstothetransferofmoisture.Thisisusuallydonebytheproperselectionof
polymericresinbinder(greaterhydrophobicityandhighercrosslinkdensity).Thisiswhyepoxyresinsareamajorsourceof
industrialcoatings.Coatingsandadhesivebasedonvinylestersratherthanmoreconventionalpolyesterhavealsobeenassociated
withtheneareliminationofosmoticblisteringinboathulls.Barrierpropertiescanalsobeenhancedbytheadditionofinsoluble
pigmentsincoatingsoradhesivesthatprovideamoretortuouspathforthemoisturetotransverse.
Foranexcellentandmuchmoredetaileddiscussionofosmoticblisteringofpaintfilmsonmetal,thereaderisdirectedtoa
comprehensivearticle(Reference4).Foradditionalreadingregardingosmoticblisteringofcoatedpolyestercomposites,thereader
isreferredtoReference1.Inthenextarticleinthisseries,wewilldiscusshowmoistureingressintoanadhesive,coating,orother
polymericmaterialcanbemeasured.
BIO
EdwardM.PetrieisthesoleproprietorofEMPSolutions,aCary,N.C.basedconsultingfirmfocusedonsolvingproblemsinthe
adhesivesandsealantsindustry.HealsoworksasatechnicalexpertforSpecialChem.Formoreinformation,visit
www.specialchem4adhesives.com.
REFERENCES
1. Antonio,S.C.,FiberglassBlistersandBarrierCoatings,OceanNavigation,No.136,March/April2004,pp.38.
2. Abeysinghe,H.P.,et.al.,SubstancesContributingtotheGenerationofOsmoticPressureinResinsandLaminates,
Composites,January1983,pp.5761.
3. Rockett,T.J.,et.al.,MethodofPreventingGelCoatBlisteringinFiberGlassReinforcedPolymers,USPatent4,724,173,
February9,1988.
4. Hare,C.H.,BlisteringofPaintFilmsonMetal,Part1:OsmoticBlistering,JournalofProtectiveCoatingsandLiners,
February1998,pp.4563.

Sharethisarticle

Moreservices

Thisarticleisfeaturedin:
Cleaning,Pretreatment&SurfacePreparationMarineTesting&Control

Commentonthisarticle

Copyright2015
ElsevierLtd.Allrightsreserved.

http://www.metalfinishing.com/view/21322/osmoticblistersincoatingsandadhesives/

2/2