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SchoolofMechanicalEngineering

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)

the uniform corrosion of ZnSn alloy in an oxygen saturated solution of cupric


chloride,stannicchlorideandhydrochloricacid

(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.

Determine halfcell potential of H electrode in aqueous solution of pH=7, under


0.5atmpartialpressureandat40C.
[0.426V]

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IndustrialCorrosionandPrevention308

TUTORIALQUESTIONS
2.6.

Giventhatthecellpotentialis+0.590VofaZnHcellina0.5MZnCl 2 solution,
determinethepHofthesolution.
[3.28]

2.7.

ApieceofZnissubmergedinCuCl2solutioninasmallcontainer.Willcorrosion
occur?Ifsowillthereactionstopeventually?Ifsounderwhatconditionwillitstop?
[[Zn2+]/[Cu2+]=1.45x1037]

Tutorial 3 - Uniform Corrosion, Galvanic Corrosion


31.

Although all forms of corrosion are undesirable, uniform corrosion is least


objectionable.Why?

32.

Canuniformcorrosionbeusedtothebenefitofcorrosionprotection?
Canuniformcorrosionbeusedtothebenefitofotherengineeringpurposes?
Givesomeexamplesifyouthinkyestotheabovetwoquestions.

33.

Whatisrust?Doesrusthaveanyeffectoncorrosion?

34.

A metal, M, of valency z, atomic mass W and density D (kgm ) is corroding


uniformly over its exposed surface by an electrochemical process with a current

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.

It is important to recognise galvanic corrosion when it happens. Consider the


followingcases:

(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)

A 10m2 lead plate contaminated byasmall drop(1mm 2)tin onits surface is


immersedinseawater.Willthisproducegalvaniccorrosion?

SchoolofMechanicalEngineering

IndustrialCorrosionandPrevention308

TUTORIALQUESTIONS
37.

Whataretheessentialconditionsforgalvaniccorrosion?

3.8.

Ifonemetalofagalvaniccoupleistobecoated,whichwouldyouchoose?Why?

3.9.

Galvanic corrosion is an electrochemical process. Is it possible to determine the


corrosionrateinthiscasebyelectricalmeasurement?Ifso,how?

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.

(1) Explain the mechanisms of this


typeofcorrosion.
(2) Writedownthepossiblecorrosion
reactions (assuming galvanised
steel container) and point out the
locationforeachreaction.

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.

What is the sensitisation of austenitic stainless steels? Can it be avoided? Once


happened,canitbeeliminated?

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.

Stresscorrosion cracking is due to the combined action of a tensile stress and


corrosiveenvironment.Inwhatwaydoesstresscorrosioncrackingdifferfrom
(i)mechanicalcracking,and
(ii)environmentalcorrosion?
Tutorial7Oxidation,HydrogenAttack

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.

What are the differences between stresscorrosion cracking and hydrogen


embrittlement? Are these differences important so far as protection measures are
concerned?

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.

A steel pipeline submerged in seawater is to be protected by impressed current


cathodicprotection.Thelengthofthepipelineis500m. Ifanodesareempirically
chosentobeplacedatadistance2mfromthepipeline,estimatethenumberofanodes
required for the protection system, given that the range of current density on the

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.

Niproducesaptypeoxide. Lihasvirtuallynoresistancetooxidation. Crisan


element invariably used in oxidationresistant alloys. What oxidation behaviour
wouldyouexpectwhenNiisalloyedwithasmallamountof(1)Liand(2)Cr?

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

Data: wettedsurfaceareaoflegs: 2000m

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)?