LubricantAnalysisinSteamTurbines

BeatrizGraa,INEGIJorgeSeabra,FEUPPintoSousa,Portucel
Tags:oilanalysis,contaminationcontrol,CaseStudies

MachineryLubrication(10/2011)

Turbineoilsaresubjectedtoawiderangeofconditionsextremeheat,entrainedair,moisture,
contaminationbydirtanddebris,inadvertentmixingwithdifferentoil,etc.thatdegradetheintegrity
ofthehydrocarbonbasestockanddepletetheadditivechemistries,causingirreversiblemolecular
changes.Therearetwoprimarydegradationmechanismsinturbineapplicationsoxidationandthermal
degradation.
Oxidationisachemicalprocesswheretheoxygenreactswiththeoilmoleculestoformanumberof
differentchemicalproducts,suchascarboxylicacids.Therateatwhichthisoccursdependsona
numberoffactors.Temperatureisperhapsthemostcriticalone,sincetherateofoxidationdoublesfor
everyriseof10degreesC.Thetemperatureabovewhichthisoccursisinfluencedbytheoxidation
stabilityoftheoilandthepresenceofcatalystsandprooxidantconditionssuchaswater,air,certain
metals,fluidagitationandpressure.
Thermaldegradationisthebreakdownoftheoilmoleculesbyheat(hightemperature),forming
insolublecompoundsthatfrequentlyarereferredtoassoftcontaminants.Typically,thermal
degradationoccursasaresultofmicrodieseling,electrostaticsparkdischargeandhotspots.Micro
dieselingisthecombustionofimplodingairbubblescreatingadiabaticcompressiveheat(often
exceedingtemperaturesabove1,000degreesC).Electrostaticsparkdischargeresultsfromtheinternal
molecularfrictionthatgenerateshighvoltageelectricchargessuchaswhereoilpassesthroughvery
tightclearancesathighflowrates,producingtemperaturesover10,000degreesC.
Overtime,ithasbecomeclearthattheoxidationperformancesofthedifferentbasestockclassesare
quitedifferent.ThehighnaturaloxidativeresistanceofGroupIIturbineoilscombinedwithspecific
antioxidantsemployed(usuallybasedinphenolandaminecompounds)provideanonlinearbehaviorin
termsoftheirmoleculardegradationovertime.Asaresult,themajorityofstandardoilanalysistests
offerlittletonowarningasthelubricantstartstodegradeandgeneratesystemdeposits.Insteadof
degradationoccurringinalinearandpredictablefashion,manyofthemodernturbineoilsfailrapidly.
Changesintheoilsmolecularstructureduetoadditivedepletionandthedevelopmentofinsoluble
particulatesareamongthefirstoildegradationconditionsthataffectequipmentperformance.The
sequentialprocesswillbetheformationofsludgeandvarnish,whicharecommonoccurrencesinturbo
generators.Besidestheseoxidationandthermaldegradationbyproductsbeingthemaincontributorsfor
thedevelopmentofvarnishanddepositproblemsinturbines,theyinterferewithotherimportant
propertiesinsteamturbinelubricants,suchasdemulsibilityandthedetrainmentofair.Therefore,itis
vitalthatappropriatediagnosticanalysisbeperformedtodetecttheseconditionsincriticaland
sensitivelubricationsystems.

Degradationtrendofdifferentbasestockoils

FerrographyAnalysis
Ferrographyisatechniquethatprovidesvaluableinformationaboutwearevolutioninmachinery
throughanalysisofarepresentativelubricantsample.DevelopedbyVernonWestcottattheU.S.Navy
inthe1970sasaconditionmonitoringtechnique,ithasbeenappliedbyhundredsofworldwideusersto
allkindsoflubricatedsystems.
Thepotentialofferrographyisnotonlylimitedtopredictive
maintenancestrategies.Itsimportantcontributionto
tribologystudies,byassistinginabetterunderstandingof
thewearmechanismsandofthelubricanteffectsonthe
contactsurfaces,turnsthisversatiletechnologyintooneof
themostpowerfuldiagnostictoolstoassessmachinehealth,
providingvaluableinformationaboutthepast,presentand
futureconditionofthemachineslubricatedcomponents.

Analyticalferrographydepositedpatterns

Thetestprocedureislengthyandrequirestheskillofawell
trainedanalyst.Assuch,therearesignificantcostsin
performinganalyticalferrographynotpresentinotheroil
analysistests.However,iftimeistakentofullyunderstand
whatanalyticalferrographyuncovers,mostagreethatthe
benefitssignificantlyoutweighthecostsandelectto
automaticallyincorporateitwhenabnormalwearis

encountered.
Inanalyticalferrography,thesoliddebrissuspendedinalubricantsampleisseparatedandthoroughly
depositedontoaglassslidewhilepassingacrossabipolarmagneticfield.Whenthesampleflowis
completed,asolventwashcycleremovesanylubricantremainingonthesubstrate,resultingina
ferrogram,wheretheparticlesareallarrangedbysizeandpermanentlyattachedtotheslidefor
opticalanalysisusingabiochromaticmicroscope.Theparticlesarethenexaminedandclassifiedby
size,shape,concentrationandmetallurgy.Thisinformationcarriedbythewearparticlesisvaluablefor
theidentificationofthewearmodeandmechanism.

SteamTurbineMonitoring

Thiscasestudyisabouttheconditionmonitoringofthelubricantinasteamturbogeneratoratalocal
celluloseindustryplant.Theturbineisa26MWSiemensG8002.Ithasbeeninservicefor22years,
operatingcontinuously,withalubricatingoilreservoirholding8,500litersofISOVG46oiltolubricate
andcoolbearings,gearsandoilshaftsealsandtoactasahydraulicmediumforoperationofthe
governorandsteamcontrolvalves.
Sinceitsinitialoperationin1988,thisturbineworkedwithsolventrefinedbasestockoil(GroupI).
However,duetoamanufacturerupgrade,thisoilwasreplacedbyahydrocrackedbasestock(GroupII)
in2002.Inthemeantime,about6,000litersofmakeupfluidwasadded,alongwithafewperiodicoil
reservoirfillups,makingthecirculatingfluidablendofthesetwobasestocks.
Theturbogeneratorwasoperatingandperformingnormally,andnooccurrencesofanomalous
functionsofthelubricatedcomponentshadbeenrecorded.Nevertheless,aclosemonitoringoftheoil
conditionwasensuredbyanalyzingtheturbineoilperiodically.

Asteamturbogeneratoratacelluloseindustryplant

TurbineOilAnalysis
Alubricantanalysisprogramwasappliedquarterly,takingtwosamplesfromtheoilreservoirand
sendingittoindependentlaboratories.Thestandardmethodsusedatoneofthelaboratoriestoassess
theconditionoftheturbineoilwere:
Kinematicviscosityat40degreesC(ASTMD445)
WaterbyKarlFisher(ASTMD6304)
Insolubleparticulates(ASTMD4898)
Acidnumber(ASTMD664)
Neutralizationnumber(ASTMD974)
Elementalspectroscopy(ASTMD5185)
Rust(ASTMD665A)
Demulsibility(IP19)
Foam(ASTMD892)
Flashpoint(ASTMD92)
Airrelease(DIN51636)

Cleanlinesscode(ISO4406)
Linearsweepvoltammetry(LSV),(ASTMD6971)
Simultaneously,atanotherlaboratory,ferrographyandFouriertransforminfrared(FTIR)analysiswere
performedalongwithothertechniques.Theseanalysesallowedacomplementeddiagnosisnotonlyof
theconditionoftheoilbutalsooftheturbinewearrateconditions.
Inthiscasestudy,amongallthestandardtestresultsobtained,thosethatshowedsomeindicationsof
fluiddegradationwerethedemulsibility,airrelease,particlecountandLSV.Ascanbeseeninthetable
above,theoilviscosityandacidnumberarewithintherangeoverthetimeperiod.Watercontamination
andfoamtendencyaremaintainedlow.However,theparticlecontaminationishighforallthe
evaluatedperiod,thephenoliccontentfallsbelowcriticalinsomesamplesandthedemulsibilityisalso
affectedsignificantly.
Thesequentialeventsintheoildegradationproducesaneventualdepletionoftheantioxidantadditives.
Theaminic/phenolicantioxidantmixturesactuateasacomplexsystem.Theaminicinhibitorworksto
neutralizethefreeradicalsthatcauseoiloxidation,butitisthenregeneratedbyphenolic,whichisa
goodfreeradicaltrap.Whenphenoliclevelsfallbelowacriticallevel,theoilisindangerofrapid
degradation,resultingintheformationofsoftcontaminantsandvarnish.Softcontaminantsaretypically
lessthan2micronsinsizeandcannotberemovedthroughstandardmechanicalfiltration.Theyare
insolubleandpolarinnature,andareunstableinanonpolaroilenvironment,suchashydrocracked
baseoil(GroupII).

Analyticalresultsfromstandardoiltestsshowtheoilviscosityandacidnumberarewithintherange
overthetimeperiod.

ThehighISOCodesobtained,mainlyintermsofsmallparticles(lessthan4microns),canberelated
withthisturbineoildegradationprocess.Demulsibilityisalsocompromisedbythepresenceofpolar
contaminants.
Forthelubricationofturbogeneratorbearings,thecleanlinesslevelwithrespecttoparticlesintheoil
isoftheutmostimportance.Consequently,aproactiveactionistakenthroughperiodicalonlineoil
purification(filtrationduring24hours)toachievethesystemcleanlinessinaccordancewithOEM
recommendations(ISO18/16/12).However,aswiftincreaseoftheISOCodesisconsistentlyverified
duringtheoperationofthisturbine.
Theferrographyanalysiscompletedforthesameperiodrevealedvaluableinformationontheoilssolid
contamination.Inallferrograms,thepresenceofsoftcontaminantsthatresultedfromoilthermal
degradationandadditivedepletionwasobserved.Thisinformationisessentialtoidentifythereasonfor
thepersistenthighISOCodesobtainedinparticlecounting.Althoughsoftparticulatesarenotharmfulin

termsofwear,theycontributetothegenerationofsurfacedeposits,asdetectedthroughferrography.
Figure1showstwophotomicrographsoftheseparticlesdepositedonaferrogramasobservedunder
white/greenlightandpolarizedillumination.Thepolarizedlightallowstheidentificationofnonmetallic
particles(crystallineandamorphousmaterials,forinstance)bythebrightnessoflightreflected.Note
thebrownpatternevidencedbysomeoftheseparticles.

Figure1.Thesetwophotomicrographsshowturbineoilcrystallinecontaminants(1,000xmagnification).
TheparticlesintheferrogramofFigure2areverysmallinsize,andduetopolarity,theyeasilyaligned
alongthemagneticfieldoftheferrograph.Theseparticleshavethetendencytoformagglomerates,
whichwhenoverstressedwiththeoil,formalargecoherentstructurebyamolecularpolymerization.
Thevarnishbuildupseemstobeaconsequenceofthis
physicochemicalprocess,ascanberealizedbythe
photomicrographsinFigure3,obtainedindifferentoil
samples.Allthesekindsofparticulateshavepolar
affinitiesandhighmolecularweightandtendtobe
adsorbedontodipolarmetallicsurfacesasasticking
matter,whichinturncaptureshardcontaminantsasthey
flowwithinthesystem.Theyarecapableofshuttingdown
aturbineorcausingseriousdamage,whichisfrequently
relatedtobearingsandservoapplications.
Anothertechniqueemployedtomonitortheoilcondition
wasFTIR,whichisusedtomeasureorganicmolecular
components,monitoradditivedepletion(antioxidants)and
identifyorganicdegradationbyproducts(oxidation).The
monitoringofspecificantioxidantdepletioninusedlubricantsisstillconsideredarelativelynew
researcharea.However,somestudiesshowthattherateofantioxidantdepletionisrelatedtolubricant
degradationoraffectedbytheantioxidantmixorbasestocktypeusedtoproducethelubricant.
Figure2.Particlesalignedontheferrogram
tothemagneticfield

Usedoilsamplesarecomplexmixturesofdifferentchemicals,includingcompoundsderivedfromthe
formulationofthebaseoilanditsadditives,andfromoildegradationproductsandcontaminants.Asa
result,ausedoilspectrumiscomplexandessentiallythenetsumofthespectraofalltheindividual
compoundsmakingupthesample.Infact,becauseofthiscomplexity,theusedoilspectrumaloneisof
limitedvalueandmustbecomparedagainstthespectrumoftheunusedoiltobeofsignificant
analyticalvalue.
Figure4showstransmittancespectralsnapshotsofthenewandusedturbineoil.Theblackspectrumis
thatofthenewoil(newbasestockGroupII),whiletheredspectrumisfromtheblendoilinservice,
whichstillcontainsasmallpercentageofGroupIbasestockoil.Nevertheless,thespectrarevealed
identicalfunctionalgroups.
Inanalyzingthespectrumoverlays,youcanclearlyseerelativemolecularchangesintheoxidation
peaks,aswellasthermaldegradationoftheoilthroughthesignsofnitration.Anothermolecular

alterationisobservedwherethephenolicantioxidantsarecharacterized.Thetypeofdecomposition
detectedintheusedoilspectrumiscommonlyobservedinFTIRanalysisoffluidswherethermal
breakdowntookplace.

Figure3.Ferrogramphotomicrographsoftheturbineoilparticlesindifferentsamples(1,000x
magnification)

Figure4.FTIRspectraintransmittance/wavenumber(cm1)ofnewandusedturbineoils

FilterAnalysis
Staticgeneratedsparksareverycommonincidentsinthefilteringsystemsofturbogenerators.Thisis
aphenomenonofmolecularfrictionoccurringasoilflowsthroughsmallclearances,suchasthefilter
media.Sinceoilandfiltermediaarebothdielectric,thiselectricalenergybuildsuntilalimitisreached,
andthensparksarereleasedinthelubricationsysteminthedirectionoftheground.Theseelectrical
arcscanhaveanextremelyhigh,localizedtemperature(about20,000degreesC),instantlycracking
thehydrocarbonmolecule.

Sincesparkdischargesgeneratedonfiltersandother
locationsareakeyrootcauseofvarnish,andsome
ofthepreviousoilanalysisresultsconfirmedthat
(throughadditivedepletionandhighparticlecounts),
oneoftheduplextypefilterswasdismantledand
analyzedthroughanopticalmicroscope.
Evidenceofelectricdischargecanbeeasilyseen
throughmicroscopicinspectionofthefiltermedia,
filtercore,filtermeshesandfromdebriscarried
awayfromthefilter.

Figure5.Pluggedfilterfromtheturbogenerator
andfiltermeshwithblackandbrown
shinyresidue(200xmagnification)

Figure5showsoneofthepluggedfilterschangedin
aperiodicmaintenanceactionduetoapluggedfilter
alarm,withamicroscopicviewofthefiltermesh.As
canbeseen,blackandbrownshinydeposits(sludge
andvarnish)arepresentinhighconcentrations,
cloggingthefiltermesh.

Thesolventusedforcleaningthefiltermeshwas
collectedandusedtoprepareaferrogramwheresignificantamountsofferroussphericalwearparticles
wereidentified(Figures6and7).Onesourceofsphericalferrousdebrisistheerosionwearactivated
byelectricaldischarges.Thehightemperaturesattainedbythesparksonthesteelsurfacethermally
liquefythesteeldebris,whichacquiresasphericalshapeduetorapidcoolingundertheactionof
surfacetension.
Themicroscopicanalysisofthefiltercoresurfaceshowedseveralsmall,circularburnedholesleftby
thehightemperaturesparkdischargesonthemetalsurfaces.
Inconclusion,turbineoilsmustbewellmaintainedtoextendtheirservicelifeandsimultaneously
providethemaximumturbineperformance.However,therecentupgradeintheturbineoilformulations
hascausedsomecontroversy.Theolderanalyticaltechniquesarenolongerthepredictivetoolsableto
monitortherealconditionthattheyoncewere.

Figure6.Photomicrographshowinghighconcentrationofferrousspheres(1,000xmagnification)tothe
magneticfield


Figure7.Photomicrographsofsmallburnedholesonthesurfacefiltercore(200xand1,000x
magnification)

Thegenerationandpresenceofsoftcontaminantsareamongthemainconsequencesoftheactual
turbineoildegradationprocess.Therearefourlikelyreasonsforthis:
Unlikeoldgenerationbaseoils(GroupI),thetypeofbaseoilcurrentlyused(GroupII)doesnot
holdvarnishprecursorsinsuspension.Theseinsolubleparticlesmayformdeposits.
GroupIandGroupIIturbineoilspossesssignificantlydifferentoxidationpropertiesandfailure
mechanisms.
Theantioxidantsprecipitateastheyarepreferentialoxidesgeneratinginsolubleparticulates.
Thenewgenerationofantifoamadditiveshaslesseffectiveairreleasecharacteristics,andthese
smallairbubblesareadiabaticallycompressed,causingvarnishtoappear.
Inthiscasestudy,itwasrecognizedthatonlythefollowingtechniquesusedtomonitortheconditionof
theturbineoilwereefficientinpredictingeminentproblemsrelatedtothegenerationofvarnishand
sludge:
Particlecounting(ISOCode)waseffectiveinmonitoringparticlecontamination.Thiswasinspite
ofthefactthatmostparticlecountersarenotsensitivetothesmallsizeofthepolarparticles
(lessthan2microns).Thereasonfortheirefficiencywasthattheparticleshaveatendencyto
formagglomerates,increasingthesizeoftheparticulatesandthusallowingparticlecountingto
detectthem.
Thedemulsibilityoftheoilwasacriticalcharacteristictoevaluatesinceitisaffectedbythe
presenceofpolarparticles.Thealterationofthispropertycouldbeasignalofextremeparticle
contamination.
TheLSVtechnologyandFTIRarebothalreadyrecognizedasimportanttechniquestomonitorthe
conditionofmodernturbineoils.Theyefficientlymonitortheconditionoftheantioxidantpackage
andthecreationofsoftcontaminants.
Analyticalferrographywaseffectiveinthedetectionofsoftcontaminantsandintheidentification
oftheirnature.Inthehandsofaskilledanalyst,analyticalferrographyisapowerfultechniqueto
identifyturbineoilrelatedproblems,providingarootcausebasedonthemorphologyand
characteristicsoftheinsolubleparticles,aswellasmonitoringtheprogressivemechanismof
varnishformation.