EstablishingElementalLimitValuesforMotorOils

Limitandwarninglevelsfromelementalspectrometric
analysisserveasindicatorsoftheamountofforeign
particlesfoundinusedoilthatisstilltolerableor,when
comparedwithfreshoil,indicatewhenthealtered
lubricantmustbechanged.Valueswellabovetolerable
wearlevelscanalsoindicateanacutedamage
process.However,itisnoteasytospecifythese
warninglevels.Hardlyanyengineorequipment
manufacturerdefineslimitlevelsforusedoil.Thisis
becausetheoperatingconditionsandtimesaretoo
specific,andtheoriginsoftheforeignparticlesfoundin
theoilaretoodiverse.Consequently,determining
thesefactorsisoneoftheessentialtasksofeveryoil
analysis.Afterall,thetype,quantityand(toacertain
extent)thesizeoftheparticlesprovidevaluable
informationaboutwear,contaminantsandthe
additivesintheoil.

Warninglevelsmustbesetlowerforgreateroilvolumes,shorteroilservicelife,lower
enginespeedandlighterloadconditions

Whenwarningandlimitlevelsareusedforthediagnosisofaspecificoilspecimen,theinteractionsbetween
thevaluesandothercriteriashouldalsobetakenintoaccount.Avarietyoffactorsplayarolehere,including
theenginemanufacturer,theenginetype,thetypeoffuelused,theoilvolume,themotoroiltype,theservice
lifeofthemotoroil,andanytopupquantities(makeupoil).Theoperatingconditionscanalsovarymarkedly
fromonesituationtothenext.Afterall,theengineofaheavyconstructionmachineoperatesunderdifferent
conditionsthanthesameengineofatrucktravelinglongdistancesonahighwayatuniformspeed.

However,alloftheseengineshaveonethingincommon:theirmotoroilcontainsalotofvaluableinformation
abouttheoilitselfaswellasthestateoftheengine.Forexample,themicroscopicparticlessuspendedinthe
oilprovideanindicationoftheamountofwearofthecorrespondingpartsorcomponents.Elementssuchas
sodium,potassiumorsiliconindicatecontaminationbyroadsalt,hardwater,glycolantifreezeordust.
Comparingtheamountoforganometallicadditiveelements(suchascalcium,magnesium,phosphorus,zinc,
sulfurorboron)intheusedoiltofreshoilprovidesanindicationofchangestotheoil,suchasadditive
depletionorpossiblythemixingofdifferenttypesofoils.
Table1.Wearelements
Element Upper Origin
Warning
Level

Iron(Fe) 80180 Cylinderblock,cylinderhead,timing

wheelsandtimingchains,valves,valve
tappetsandguides,crankshaft,
camshaft,rockerarmshaft,pistonpins,
rollerbearings(withchromium),oil
pumprareinresiduesofferrocene,a
fueladditiveforsootreduction
distinguishingbetweencorrosionand
wearbasedonthePQindex
Chromium 428 Pistonrings,crankshaftbearings,
(Cr) pistonpins,exhaustvalves,gaskets,
guidebushes,chromeplatedpartsand
gearsFe,AlandCrareusuallyfound
incombinationwithSiinengines
becausedustcausesthemostpiston
(Al),pistonring(Cr)andcylinder(Fe)
wear

Tin(Sn) 1224 Oftentogetherwithlead(Babbitt

bearings)orcopperrunningsurfaces
ofconnectingrodbearings,rockerarm
shaftandpistonpinbearings,solder
(consistingofleadandtin)insoldered
radiatorjointsconstituentofsome
syntheticbaseoils,additivesinfire
resistantfluids

Aluminum 1255 Primarilyfrompistons,oilpump

(Al) housings,oilcoolers,torqueconverter
parts,turbocharger,guidebushes,
plainbearings,cylinderblocksofall
aluminumengines(togetherwith
silicon)anddustcontainingbauxite
(aluminumoxide)

Nickel(Ni) 13 Alloyconstituentofexhaustvalves,
valveguides,turbochargers,high
strengthgearsandturbineblades
insteadofbeinggalvanizedorchrome
plated,partssuchasfiltercomponents
maybenickelplatedconstituentof
heavyoil(togetherwithvanadium)

Copper(Cu) 2560 Mainconstituentofbrassandbronze

aswearmetalfromoilpumps,
connectingrodbearings,pistonpin
bearings,rockerarmshaftbearings,
bronzewormgears,andsinteredbrake
andclutchdiscsresultingfromthe
corrosionofoilcoolers,pipingand
seals

Lead(Pb) 1030 Usuallyincombinationwithtinand/or

copperconnectingrodbearings,
nearlyallrunningsurfacesofplain
bearingsandsolderedjointsin
combinationwithtin
 Molybdenum 420Up Containedintransmissionsynchronizer
(Mo) to500in rings,pistonringsandheatresistant
freshoil steelscomponentofanantioxidant
andfrictionmodifieradditivepackage
inmodernsyntheticmultigradeoilsand
gearoilsrarelyasMoS2oiladditives

Inductivelycoupledplasma(ICP)elementalanalysiscanbeusedtodeterminemorethan30different
elementsinmotoroils.Inadditiontothepresenceoftheelements,atomicemissionspectroscopy(AES)by
ICPcanbeusedtodeterminetheconcentrationsoftheelements.

Laboratoriesroutinelydeterminethefollowingelementsandvaluesaspartofmotoroiltestingandlistthemin
thelabreport:iron,chromium,tin,aluminum,nickel,copper,lead,calcium,magnesium,boron,zinc,
phosphorus,barium,molybdenum,sulfur,silicon,sodiumandpotassium.Insomecases,otherelementsare
alsodetermined,suchassilver,vanadium,tungstenorceramicelementslikeceriumandberyllium,whichare
rarelypresentinmotoroils.Theyareonlylistedinthelabreportiftheyareactuallyproventobepresentorif
thecustomerspecificallyrequeststhis.Tables13showthepossiblecausesforthepresenceoftheelements
foundinoil,i.e.,whethertheyarerelatedtocontaminants,wearoradditives.
Table2.Contaminants
Silicon(Si) 15 Intakeairdust,antifoamadditiveinmotor
30 oil,wornsealscontainingsilicone,residues
Up ofsiliconegreases(alsoinoilsampling
to15 syringes),wornaluminumalloys(aluminum
in engines)
fresh
oil

Potassium 230 Additiveinaqueousmediasuchasglycol

(K) antifreezeorcoolingwatermineralsaltin
roadsaltortapwater

Sodium 530 Additiveinglycolantifreezeorcoolingwater

(Na) Up roadsalt,tapwater,wastewaterorsaltyair
to additivecomponentsinsomemotoroilsasa
800 substituteforcalciumormagnesium
in compoundsthickenerinlubricatinggreases
fresh
oil

Lithium(Li) 210 Constituentofmultipurposegreases

(thickener)indicationofcontaminationby
greaseorassemblypastes

Antimony 13 Presentinsomelubricatinggreasesasan
(Sb) EPadditiveintheformofantimonyoxidein
connectionwithleadortininbearingalloys
ofplainbearings

Silver(Ag) 13 Silverplatedrunningsurfacesofhighly
loadedplainbearings,suchasinlocomotive
 enginessilversolderresiduessilveris
attackedbyadditivesystemscontainingzinc

Tungsten 12 Rareinengineconstructionalloyconstituent
(W) forincreasinghardnessandcorrosion
resistance

Titanium 13 Oillevelindicator(float)alloyconstituentin
(Ti) springsandvalvesfromceramic
componentsaswhitetitaniumoxidein
plasticsandpaintsmarkeradditiveinmotor
oils

Vanadium 13 Asaconstituentofchromevanadiumsteel
(V) alloysinvalvesandvalvespringslike
nickel,itisaconstituentofpetroleumblow
byproductwhenshipenginesare

Beryllium 13 Cubevalvesandvalveseatssintered
(Be) bearings,constituentsofsinteredceramic
componentsorinjetengineoilsprohibited
inF1enginesoperatedwithheavyoilfuels

Cadmium 13 Componentsofplainbearingsexposedto
(Cd) corrosionsometimesalsodeepred
pigmentsinplasticsandpaints

Cobalt(Co) 13 Possiblyfromcomponentsofturbinesor
fromrollerbearingalloysinconnectionwith
iron

Manganese 13 Alloyingelement,usuallywithironsteel
(Mn) usedinvalves,rollerbearings,gearsor
shaftscontaminantinmanganesemines
(withSi)veryrarelyadditivescontaining
manganese

Tantalum Onlyfoundinoilasaconstituentofceramic
(Ta) components

Cerium Onlyfoundinoilasaconstituentofceramic
(Ce) components

Zirconium Onlyfoundinoilasaconstituentofceramic
(Zr) components

Variousfactorsmustbetakenintoaccountwheninterpretingalabreportandthevaluesoftheelementsfound
intheoil.Naturally,itisnotsufficienttosimplyreporttheelementsandtheirquantities.Inordertoassessthe
measuredvalues,youmustknowwhethertheindividualelementsindicatecontamination,wearorchangesto
theadditives.However,thesevaluesarealsointerrelatedtoacertainextent.Therelativeproportionofvarious
wearelementsprovidesanindicationoftheaffectedmachinepartsorcomponents,forexample.Further,itis
importanttoknowhowlongithastakenfortheoiltobecomeenrichedwithspecificwearelementssincethe
lastoilchange.Theoperatingtimeoftheoverallsystemortherunningtimeoftheengine,theoilvolume
relativetotheenginepower,andthetopupamountsmustalsobeconsideredwhenanalyzingordiagnosing
warninglevels.

Inordertoreliablyassessthevaluesdeterminedfortheusedoilandtheirrelationshiptoeachotherandto
otherfactors,itisnecessarytohaveasuitablylargevolumeofdataandanalyticalexpertise.However,additive
elementsandbaseoiltypescandifferconsiderablydependingonthetypeofoilused,soitisnecessarytoset
suitablybroadwarninglevels.Specificwarninglevelscanonlybedefinedforaspecificoiltype.

Table3.Additives
Calcium 600 Oiladditive,detergentoiladditive
(Ca) 5,000 improvescleaninganddispersioncapacity
aswellasheatresistanceoccasionally
calciumcontainingdustfrombuildingsites,
lubricatinggreaseconstituent,orfrom
coolingwaterortapwatercontaining
calcium

Magnesium 100 Oiladditiveimprovesthecorrosion

(Mg) 1,500 protection,thermalstabilityanddispersion
capacityofmotoroilsincreasesthealkali
reserve(BN)alloyconstituentofengine
blockshardeningagentinhardtapwater
orsaltwater

Boron(B) 10 Improvesenginecleanlinessasanoil
500 additiveboratesareconstituentsofcooler
antifreezeandcorrosionprotectionmedia

Zinc(Zn) Upto Improveswearprotectionasanoiladditive

2,000 zincplatedcomponentssuchasfilter
in supportcores,threadedfittings,paints
fresh containingzincandvulcanizedsynthetic
oil materials

Phosphorus 600 Oiladditiveinalmostalltypesofoilused

(P) 2,000 toimproveEPcharacteristicsandreduce
wearhasananticorrosionandanti
bacterialeffectreducesfrictionrenders
metalsurfaceschemicallyinert

Barium(Ba) 220 Usuallynotanadditiveinmotoroilsfor

improvingEPcharacteristicsfriction
modifierinATFsintheformofbarium
complexsoapaconstituentofgreases
andassemblypastes

Sulfur(S) 500 Constituentofbaseoilsbasedonmineral

6,000 oilforthisreason,itispresentinalmostall
 oils,butinwidelyvaryingamountsalong
withphosphorus,sulfurisalsoa
constituentofalmostalladditivepackages
forwearandcorrosionprotection,andis
oftenfoundinconnectionwithcalciumand
zinc

ThewarningandlimitlevelslistedinTables13forwearelements,contaminantsandadditivesarebasedona
semisyntheticmotoroil(SAE10W40)inamoderndieselenginewithanoilvolumeofapproximately25to50
liters,usingfuelcompliantwithEN590(containing5percentfattyacidmethylesters),andwithanoilservice
lifeofapproximately500operatinghoursoramileageofapproximately47,000miles.

Thebasicruleisthatwarninglevelsmustbesetlowerforgreateroilvolume,shorteroilservicelife,lower
enginespeedandlighterloadconditions.

However,thestatedvaluesaredistinctlydependentontheoilmanufacturer,thecorrectenginetype,the
servicelifeoftheoilcharge,theoilvolumeandthetopupquantities(ifany).

AbouttheAuthor
SteffenBots
OELCHECKGmbh