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IndustrialCorrosionandPrevention308
TUTORIALQUESTIONS
Tutorial1ElectrochemicalFundamentalsandPourbaixdiagram
1.1.
Writeelectrochemicalequationsfortheoxidationandreductionprocesseswhichmay
occurduring:
(a)
(b)
(c)
(d)
thecorrosionofaluminiumbyairfreesulphuricacid.
corrosionofironinaeratedsulphuricacidcontainingferricsulphate.
corrosionofcopperinaeratedsulphuricacidcontainingferricsulphate.
theuniformcorrosionofzinctinalloy inanoxygensaturated solution of
cupricchloride,stannicchlorideandhydrochloricacid.
(e) corrosionofsilverinanaeratedsolutionofcupricchloride,stannicchloride
andhydrochloricacid.
(f) corrosionofnickelinseawater.
(g) corrosionofironinairfreeferricchloridesolution.
1.2.
Expressthestandardelectrodepotential,Eo,ofametalintermsofthestandardGibbs
freeenergychangeGo.HencecalculatethevalueofGoatstandardtemperatureand
pressureforthecorrosionofironassumingadivalentreaction.
1.3.
IronisconnectedtocopperandthenimmersedinasolutioncontainingbothFe 2+and
Cu2+ions
(a) Whichmetalcorrodes?
(b) Write equations to describe the reactions that occur at each electrode,
assumingeachmetalhasavalencyof2.
(c) Calculatethemaximumpossiblepotentialoftheresultingcorrosioncell.
1.4.
Calculatetherestpotential,versusthesaturatedcalomelelectrode(SCE),ofapieceof
copperinequilibriumwithasolutioncontaining106Mcopper(II)ions.
1.5.
UsethedataprovidedtoconstructacompositeFeH 2OPourbaixdiagramshowingthe
areasofstabilityofsolids(Fe,Fe3O4andFe2O3)andionicspecies(Fe2+andFe3+)for1
moleperlitreofdissolvedions.Alsodrawtheareasofstabilityfor10 6moleperlitre
ofdissolvedions.Brieflyexplainhowthestabilityareasaredesignatedtorespective
species.Thestandardfreeenergiesofformationofvarioussolidsandionicspeciesat
298Kareasfollows(valueincal/mol):
Fe2+
20300 Fe
H+
SchoolofMechanicalEngineering
IndustrialCorrosionandPrevention308
TUTORIALQUESTIONS
Fe3+
1.6.
2530
Fe3O4
242400
Fe2O3
177100
H2O
56690
UsingtheattachedPourbaixdiagramforthetinwatersystem,answerthefollowing
questions:
(a) Whattypeofequilibriumreactionsisrepresentedbythedashedlinesandwhat
arerepresentedbythesolidonesinthediagram?
(b) Whydoweseethreetypesoflines,horizontal,verticalandinclined,inthe
diagram?
(c) Whatisthemeaningoftheinterceptpointoflines2',3'and4'? Writethe
equilibriumreactionforeachline.
(d) Wouldyouexpecttintobestableinanaqueous,oxygenfreeacidsolution
withapH=1.0thatcontains106 Moftinion? Explainyouranswersand
writethehalfcellreactionsandoverallreactionsthatwouldoccur.
(e) Tincoatedcansarecommonlyusedtocontainslightlyacidicfoodproducts.
Using the enclosed Pourbaix diagram, schematically sketch the expected
corrosionrateoftininanaqueoussolutionasafunctionofpHataconstant
potentialofE=0.Writethecorrosionreactionforanyregionofhighcorrosion
rate.
(f) Indicateinthediagram,theregionsofcorrosion,immunityandpassivationfor
tininwaterat25C.
Figure1.Pourbaixdiagramforthetinwatersystemat25oC
SchoolofMechanicalEngineering
IndustrialCorrosionandPrevention308
TUTORIALQUESTIONS
Tutorial2ElectrochemicalFundamentalsofCorrosion
2.1.
Writeelectrochemicalequationsfortheoxidationandreductionprocessesoccurring
during:
(a)
thecorrosionofAlinairfreesulphuricacid
(b)
thecorrosionofFeinaeratedsulphuricacidcontainingferricsulphate
(c)
thecorrosionofCuinaeratedsulphuricacidcontainingferricsulphate
(d)
(e)
thecorrosionofAginanaeratedsolutionofcupericchloride,stannicchlorideand
hydrochloricacid
(f)
thecorrosionofNiinseawater
(g)
thecorrosionofFeinairfreeferricchloridesolution
2.2.
Drawakineticdiagram(Evslogi)formetalMcorrodinginanacidsolutionunder
activation control. Label carefully and indicate the corrosion rate of this system
(icorr).Willcorrosionratebeincreasedordecreasedbythefollowingchanges:
(a)
increasingiooftheMM++ereaction?
(b)
increasingioofthe2H++2eH2reaction?
(c)
shiftingthereversiblepotentialtoamorenoble(+)value?
(d)
increasingthevalueoffortheoxidationreaction?
2.3.
Atypicalactivepassivemetalispassivatedbyplacingitinasolutioncontaininga
largequantityofoxidisingagent.Forsuchasystemwhathappenstocorrosionrate
during
(a)
anodicpolarisationand
(b)
cathodicpolarisation?
2.4.
DeterminehalfcellpotentialofZnelectrodeina0.01MZnCl2aqueoussolution.
[0.827V]
2.5.
SchoolofMechanicalEngineering
IndustrialCorrosionandPrevention308
TUTORIALQUESTIONS
2.6.
Giventhatthecellpotentialis+0.590VofaZnHcellina0.5MZnCl 2 solution,
determinethepHofthesolution.
[3.28]
2.7.
ApieceofZnissubmergedinCuCl2solutioninasmallcontainer.Willcorrosion
occur?Ifsowillthereactionstopeventually?Ifsounderwhatconditionwillitstop?
[[Zn2+]/[Cu2+]=1.45x1037]
32.
Canuniformcorrosionbeusedtothebenefitofcorrosionprotection?
Canuniformcorrosionbeusedtothebenefitofotherengineeringpurposes?
Givesomeexamplesifyouthinkyestotheabovetwoquestions.
33.
Whatisrust?Doesrusthaveanyeffectoncorrosion?
34.
densityoficorr(Am ).Deriveanexpressionofcorrosionrateinmmpyofthemetal,
assumingthatthebuildupofcorrosionproductdoesnotstopthecorrosionreaction.
2
If the metal is Cu and the corrosion current density is 0.01 Am , calculate the
corrosionrate.(0.0116mmpy)
35.
Therateofuniformcorrosioncanalsobeexperimentallydeterminedbymeasuring
weightlossoveraperiodoftime. Deriveanexpressionoftherateofcorrosionin
mmpy using data from such a measurement. (Identify every variable in your
equations). Discuss the similarities and differences between this method and the
methoddealtwithinquestion3.4
36.
(a)
Itisnoticedthatamagnesiumdrainpluginthesteeloilpanofanautomobileis
visiblycorrodedontheinside(oilside).Isthisanexampleofgalvaniccorrosion?
(b)
EqualareasofcopperandMonelsheetboltedtogether(Monelnutsandbolts)are
immersedinseawaterforoneyear.Inspectionshowssomegeneralcorrosionofthe
copper and no visible attack of the Monel. Is this a classical case of galvanic
corrosion?
(c)
Duringanimaltestingofalloysforsurgicalimplants,mostproceduresrecommend
thatonlyonetypeofmetalbetestedineachanimaltoavoidgalvaniccorrosioneven
thoughthespecimensarephysicallyseparated.Isthisareasonablecriterion?
(d)
SchoolofMechanicalEngineering
IndustrialCorrosionandPrevention308
TUTORIALQUESTIONS
37.
Whataretheessentialconditionsforgalvaniccorrosion?
3.8.
Ifonemetalofagalvaniccoupleistobecoated,whichwouldyouchoose?Why?
3.9.
310. CanacomprehensiveEMFtableservetheneedsforpredictingindustrialgalvanic
corrosion?Whyorwhynot?
311. Ononehanditisknownthatrelativeelectrodepotentialsaretransferable,ontheother
itisrecommendedthatgalvanictestistobecarriedoutforagivencouplinginagiven
environmentwheneverpossible.Istherecommendationreallynecessary?
3.12
Estimatethecritical[Sn2+]/[Fe2+]ratioatwhichSnisgalvanicallycorrodedbyFeat
roomtemperature.
3.13
Apieceofgalvanisedsteelissubmergedinasmallcontainercontainingtapwaterat
roomtemperature.Willthesteelcorrode?Ifso,isitpossibletoidentifythecondition
numerically?Willthesituationbedifferentifitwasalargecontainer?
3.14
Seacoastallocationsaregenerallymorecorrosivethaninlandareas. Doesgalvanic
effectcontributetocorrosioninthiscaseandwhy?
3.15
ACuplatehasanexposureareaof7430cm2.Intheplatethereare5steelrivets,each
withanexposureareaof0.64cm2.Theassemblyissubmergedinanelectrolyteina
sealedcontainerwithpurgingN2.Ifthecorrosionrateofthesteelinthesolutionis
0.156mm/ywhenuncoupled:
(1) Determinethecorrosionrateofthesteelrivets.
[77mm/y]
(2) Ifitwasasteelplatewith5Curivets,whatwouldbetocorrosionrateof
thesteelplate?
SchoolofMechanicalEngineering
IndustrialCorrosionandPrevention308
TUTORIALQUESTIONS
Tutorial4Crevice,Corrosion,PittingCorrosion
41.
ExplainhowcrevicecorrosionisacceleratedbythemigrationofClintothecrevice.
42.
Explainwhycrevicecorrosionisparticularlydifficulttodetect.
43.
Describetheautocatalyticnatureofpittingcorrosion.
44.
Commentonthemaximumandaveragepitdepthmeasurementsasmeanstoevaluate
pittingcorrosion.
45.
Aqueous storage containers are often found to corrode just under the water line
(location(c)).Thisformofcorrosioniscommonlyknownaswaterlinecorrosion.
water line
b
c
d
(3) Howcanthisformofcorrosionbe
avoided?
46.
Write the possible corrosion reactions for situation (a) and (c) shown below and
predictwhichofthethreeZnsamplesislikelytocorrodemorequickly?Explainyour
prediction.WhatwouldbeyourpredictionifthesampleswereAl?
Zn
rain water
rain water
(b)
Zn
47.
Zn
rain water
air
(c)
(a)
Twoplates ofmildsteelareboltedtogetherwithasmallgapbetweenthembya
plasticbolt.Explainwhatislikelytohappenifthepairisplacedin
SchoolofMechanicalEngineering
IndustrialCorrosionandPrevention308
TUTORIALQUESTIONS
(a) neutralwater
(b) seawater
Iftheplatesareofanausteniticstainlesssteel,whatislikelytohappen?
48.
Two type 304 stainless steel plates are bolted together to form a crevice. The
assemblyisplacedinacontainerfilledwithartificialseawater.Explainthecorrosion
processatlocationAinthefollowingsituations(ignoretheoxidationofFe2+toFe3+):
(1)
Theassemblyisimmersedandthenthecreviceissealedoffbyanimaginarygateat
theopeningofthecrevice(a).
(2)
Thegateisliftedafteraprolongedperiodoftime(b).
gate lifted
gate closed
A
(a)
A
(b)
SchoolofMechanicalEngineering
IndustrialCorrosionandPrevention308
TUTORIALQUESTIONS
Tutorial5IntergranularCorrosion,SelectiveLeaching,ErosionCorrosion
51.
52.
Whatiswelddecay?Canitbeavoided?Oncehappened,canitbeeliminated?
53.
Wouldyourecommendtheuseoftype347weldingrodtoweldtype304sheetto
avoidintergranularcorrosion?Why?Ifithastobeanausteniticstainlesssteel,which
steelwouldyourecommendtoavoidtheproblemofwelddecay?
54.
Aretype347and321stainlesssteelsimmunetosensitisation?
55.
Describetwoexamples ofmetallurgicalmicrostructurehavingsignificanteffecton
corrosionresistance.
56.
What is the graphitisation of grey iron? What an alternative material would you
recommend to replace a grey iron underground pipeline to avoid/minimise the
problemofgraphitisation?
57.
Whatisthedezincificationofbrass?Doeseverybrassdezincifyequallyunderagiven
condition?Ifithastobeabrass,whichbrasswouldyouchoosetoavoidtheproblem
ofdezincification?
58.
Onearguesthatadezincifiedbrassisjustabrasswithlesszincanditshouldnot
behavewithanydifferencefromalowzincbrass.Howwouldyoucommentonthis?
59.
Whyismostdamagesufferedbytheleadingedgeofpropellers?
510. Discusstheeffectofflowvelocityoncorrosion.
511. Listthreewaystopreventerosioncorrosion.
512. Erosion corrosion is due to the combined action of a corrosive environment and
mechanicalabrasion.Inwhatwaydoesitdifferfrom
(i)mechanicalerosion,and
(ii)environmentalcorrosion?
SchoolofMechanicalEngineering
IndustrialCorrosionandPrevention308
TUTORIALQUESTIONS
Tutorial6StressCorrosionCracking,CorrosionFatigue
61.
Whateffectdoesstresscyclingfrequencyhaveonacorrosionfatiguetest?
62.
Howdoseincreasedrelativeslipbetweentwometalsaffectfrettingcorrosion?
63.
Whatisthewedgingeffectofcorrosionproducts?
64.
71.
CommentontheuseofPillingBedworthratioasacriterionforoxidationresistance.
List desirable properties of a scale for good protection against high temperature
oxidation.
72.
Hightemperatureoxidationisregardedinanaloguetoaqueousgalvaniccorrosion.
Commentonthedifferencesinmeasuresforpreventionofdeteriorationinthesetwo
cases.
73.
Whatarentypeoxidesandwhatareptypeoxides?Whatisdopingeffect?
74.
Explainthefollowingobservation:
(1)TheoxidationrateofNiisobserveddecrease afterbeingalloyed withLiand
increaseafterbeingalloyedwithCr.
(2)The oxidation rate ofZnisobservedincreaseafterbeingalloyed withLiand
decreaseafterbeingalloyedwithAl.
76.
SchoolofMechanicalEngineering
IndustrialCorrosionandPrevention308
TUTORIALQUESTIONS
Tutorial8CorrosionMonitoringandTesting
81.
Whatistheplannedintervaltest?Whatinformationcanyougetfromsuchatest?
82.
Comparethesuitabilityandlimitationsofthefollowingcorrosionratemonitoring
techniques:
(1)couponinsertion
(2)electricalresistanceprobe
(3)linearpolarisationmethod
83.
Howiscrevicecorrosionmeasuredandhowiscrevicecorrosiontendencyevaluated?
84.
Whattechniquescanyouusetomonitorthewallthicknessreductionduetocorrosion
ofaslurrypipeline?
8.5.
Explaindifferentsetupsforstresscorrosioncrackingtesting.
8.6.
Thetendencyorresistanceofamaterialtowardstresscorrosioncrackingcanbetested
inanumberofways,includingconstantstraintest,constantloadtestandslowstrain
rate test. List the parameters that can be determined to evaluate stress corrosion
crackingtendency/resistanceinthesetests. Commentonthemeritsanddemeritsof
themethods.
8.7.
Itisimportanttohaveastandard,wellplannedproceduretocarryoutacorrosion
failureanalysis. Listtheessentialstepsoftheprocedureforacomponentfailedon
site for the following three stages of analysis: on site inspection, laboratory test,
evaluationandreporting.
8.8.
Canhydrogenattackbedetected?Ifyes,how?
SchoolofMechanicalEngineering
IndustrialCorrosionandPrevention308
TUTORIALQUESTIONS
Tutorial9CorrosionControl
91.
Asteellockgateistobeprotectedusingaluminiumsacrificialanodes.Theanodesare
barsof125mmby500mmwithasteelcoreforweldingtothestructure.Determine
thefollowingparametersfortheprotectionsystemandanswerquestion(4):
(1)
(2)
(3)
(4)
minimumnumberofanodesrequired.
numberofyearstheseanodesmayprovidesufficientprotection.
minimumnumberofanodesrequiredtoprovidesufficientprotectionfor10
years.
Isoverprotectionaconcernifyouusethenumberofanodesascalculatedin
(3)?
Data: dimensionsoflockgate:
92
width: 12m
Waterlineheight:8m(upperstream)
3m(lowerstream)
2
currentrequiredforprotection:
130mAm
maximumcurrentoutputofaluminiumanode:
6.5Am
volumeconsumptionrateofaluminiumanode:
anodicefficiencyofaluminiumanode:
1180mlA y
65%
2
1 1
Ifametaliscorrodinginanacidicsolutionataratecorrespondingtoacurrentdensity
i,bytheapplicationofacathodiccurrentofthesamedensitymagnitudewill
(1)thecorrosionofthemetalbesuppressed
(2)therateofthecorrosionbereduced
(3)therateofthecorrosionbeincreased?
Explainyouranswerusingadiagram.
93.
Calculatethetheoreticalcapacityofzincsacrificialanodematerial. Themeasured
1
capacity of a zinc anode is 780 Ahkg . Calculate the efficiency of the metal.
Calculatetheconsumptionrateofthezincanode.
(819Ahkg )
94.
Usingagraph,explainschematicallyatwhatcurrentdensitywillanaluminiumanode
beconsumedifitisusedtoprotectanundergroundcarbonsteelpipeline.
3.10.
ExplainwhyonlyDCisusedforimpressedcurrentcathodicprotection.
96.
Youareaskedtodesignforacathodicprotectionsystemusingsacrificialanodesfor
anunderseastructure.Whatinformationwouldyouneed?
9.7.
Youareaskedtodesignacathodicprotectionsystemusingimpressedcurrentforan
undergroundpipeline.Whatinformationwouldyouneed?
9.8.
SchoolofMechanicalEngineering
IndustrialCorrosionandPrevention308
TUTORIALQUESTIONS
structureforproperprotectionis90~160mAm2.Assumetheelectricalresistivityof
seawateris20cm.
Itisdesirabletohavefeweranodesforeasyinstallationandmaintenance.Whatcan
youdotoreducethenumberofanodes?Whataretheimplicationsandconcernsof
thesechanges?
9.9.
Acurrentof10Aischargedintoasteelwaterpipeandleavesitatanintervalof20m.
Thepipehasanexteriordiameterof50mmandawallthicknessof1.25mm.
(a) Predictthecorrosionbehaviourofthispipe.
(b) Assumingtheelectricalresistivityofthesteelis10 5cmandtheresistivityof
wateris104cm,estimatethetotalannualmetallossduetocorrosion.
(c) Estimatethetotalannualmetal lossduetocorrosionifthemediaisseawater,
whichhasaresistivityof20cm.
SchoolofMechanicalEngineering
IndustrialCorrosionandPrevention308
TUTORIALQUESTIONS
otherquestions
75.
91.
Itisplannedtoplaceanuncoatedsteeldrillingplatforminthesea. Theimmersed
parts of the structure will be protected with an aluminium alloy (Galvalum I)
sacrificialanodeforcathodicprotectionforalifetimeof10years.Theanodesareto
besemicylindricalwithadiameterof100mm,alengthof400mmandasteelcore
forweldingtheplanesidetothestructure. Calculatethefollowingparameters(in
yourcalculationtheends,thebackandthesteelcoremaybeignored):
(1) minimumnumberofanodesrequired.
(2) numberofyearstheseanodesmayprovidesufficientprotection.
(3) minimum number of anodes required to provide sufficient protection
throughout thedesignedlifetimeof10years.
2
wettedsurfaceareaofcrossmembers:
currentrequiredforprotection:
500m
2
110mAm
maximumcurrentoutputofGalvalumI:
6.5Am
1 1
volumeconsumptionrateofGalvalumI: 1180mlA y
anodicefficiencyofGalvalumI: 60%
96.
Anoffshoreoilandgascompanyhasasectionofacarbonsteelpipelinelocatedin
seawater. ThesectionistobeprotectedusingsemicylindricalMganodes. Tryto
sketchadesignoftheprotectionsystemandestimatethenumberofanodesnecessary
toprovideadequateprotectionforaperiodof5years.Theprotectionspecifications
are as following (assuming pure Mg anodes and ignoring the ends and back of
anodes):
lengthofpipelinetobeprotected:
outsidediameterofpipe:
currentrequiredforprotection:
dimensionsofMganode:
anodemaximumcurrentoutput:
1.5km
600mm
100mA/m2
20x45mm
4.1A/m2
Ifthepipelinewasburiedundergroundhowwouldyoumodifyyourdesign(sketchonly)?