Name:LuisLozadaTipan

Unit2PrinciplesofCorrosionMATS63351
HighTemperatureOxidationofMetals
a)Statefivepropertiesofanidealprotectivehightemperaturemetaloxidescale.
1. T Oxide should create a protective scale layer: prevents access of oxygen to the metal
surfaceduetononporouscontinuousstructureoftheoxidelayer.Theformedoxidemust
notbevolatileinhightemperature.
2.Theoxideshouldhavesimilarmechanicalpropertiesasthemetal.Theoxideshouldendure
thesamestressasthemetal.Henceitspropertiesshouldbesimilarasthemetal.Moreover
theoxideshouldbestressfreeanddefectfree(noporesorcracks)
3. The oxide should be not evaporated in high temperature. The oxide film on the metal
surfaceshouldprotectthemetal.Iftheoxideisevaporated,themetalwillbeincontactwith
theenvironmentandoxidationandevaporationwillrepeatconstantly.
4.Theoxideshouldbeslowgrowinginhightemperature.Ifthemetalhasaslowoxidation
rate,theformedoxidefilmwillprotectthemetalwithoutdepletingmoremetal.
5.Endurethermalcycleswithoutspallation.Iftheoxidespall,themetalwillexposetothe
environment,whichprovokesmoreoxidationandlossesofmetalaswell.
b)Thegraphsbelowareaschematicrepresentationofweightchangeperunitareaversus
timeplotsfortheoxidationoffivedifferentpuremetalsoxidisedinpureoxygenat850C.
Foreachplotsuggestapuremetalthatwouldgivetheobservedresponseandineachcase
explainthemechanismpfoxidationforthatmetalthatleadtotheresponse.

a)IronOxidation.
Ironhasthreestablesoxidesin850C,thehigheroxide(Fe2O3)islocatedontheoutsideof
thescale.Thenextoxide(Fe3O4)isverythin.Theinneroxide(FeO)isathickoxidebutrapidly
growinglayer.TheFeOconsumesrapidlytheouterlayerbecauseitisaverymetaldeficient
ptypeoxidewithalotofcationvacancies.Thisvacanciesgeneratefastmobilityofcations
and electrons, therefore it has a very high oxidation rate, which follows a pseudolinear
oxidationrate.

b)NiobiumOxidation
The graphic b) shows initially a protective oxide layer (parabolic), then a fast oxidation
(pseudolinear),becausetheprotectiveoxidelayerwasremoved.
Niobium forms many oxides, however in high temperature it forms only one stable Oxide
Nb2O3,whichisanntypemetaloxide.Itgrowsbyinwardoxygenionsdiffusionviaanion
vacancies.Thisoxidehashighporosityinitsstructurewhichallowsahighrateofoxidation.
Oxygen dissolves in niobium surface, which provokes surface stresses to promote either
crackingoftheoxideorspallingoftheoxidefromthealloysubstrates.

c)CupperOxidation
Cupper forms ptype oxides, which are multilayered scale at elevated temperatures. The
outerlayerCuOisathinoxideandtheinnerlayerCu2Oisatickoxide.Theinneroxideshields
the metal in high temperature. Oxide copper has a large number of vacancies so that it
presentsahighoxidationrateatthebeginningoftheoxidation.Butwhentheinneroxideis
formed,thisinnerlayershieldsthemetalandtherateofoxidationbecomestosteadyrateof
oxidation.Hencethecopperoxideshowsaparabolicbehaviourat850C.

d)NickelOxidation
NickelhasonestableoxideNiO,whichisPtypeoxide,metaldeficient.TheNickelcationNi2+
across the scale to form oxide. The linear thermal expansion coefficients (LTEC) between
nickeloxideandNimetalaresimilar.HenceNiOcanendurethermalcyclingconditionwithout
brokingitsoxide.Theoxideshieldsthemetalandtheoxidedoesntallowtolosematerial.
Thenickeloxidefollowstheparabolickinetics.

e)MolybdenumOxidation
Molybdenumhasahighvapourpressureandevaporationcanoccurattemperaturesabove
400C, hence molybdenum oxide disappears in 850C. Molybdenum has several oxides
howeverMoO3isthemostimportant.Whenmolybdenumbeginsoxidizing,itcreatesaMoO3
onthesurface.However,MoO3formedonthesurfaceevaporatesalmostinstantaneouslyin
850C, The rate of oxidation is controlled by transport of oxygen to the surface, which
promotesrapidlyoxidationofthemetal.

c)Explainwhyoxidationrateincreaseswiththetemperaturefortheoxidationofnickel.
Increasing the temperature increases the diffusion of reactants. The rate of oxidation is
usuallycontrolledbytherateofdiffusionofreactants(metalionsoroxygen)acrossthemetal
oxidescale.Thereisanexponentialrelationshipbetweentemperatureanddiffusionrate.The
diffusionrateofreactants(

, )acrossthescaleisdependentontemperature.

exp

Where:
Kistheoxidationrateconstant.
Tisatemperature(K)
Aisaconstant
Qistheactivationenergy
Risthegasconstant
Kistheoxidationrateconstantandoxidationratedependantofthiskconstant.Therefore
increasingthetemperatureincreasestheoxidationrate
d)SketchanEllinghamdiagramandmarkontherelativepositionsofNO,Cr2O3andAl2O3
lines.

e)Usingthedataobtainedinthelaboratoryclass,plotgraphsofmasschangeperunitarea
versustimefortheoxidationofthecopperandnickelsamples.Explainsimplythereasons
forthedifferenceinoxidationrateforthetwomaterials.


Tiempo(min)

NickelW(mg/mm2)

CopperW(mg/mm2)

0
30
60
90

0.0000
0.0024
0.0029
0.0032

0.000
0.034
0.098
0.147

Thenickeloxideformedonthenickelsurfacewasverystableanditcouldresistthecycling
thermalconditionwithoutspallingorbreakingitsscale.Thenickeloxideshowsaparabolic
oxidationbecauseitsformedscaleshieldthemetal.

Ontheotherhand,copperandcopperoxidehavealargedifferentexpansioncoefficients.On
cooling the oxide undergoes compressive stresses, which provokes spalling of its scale.
Withoutitsscaletheoxidationrateincreasedrapidlybecauseineverythermalcyclingthe
specie should create again a new oxide and it should dissolve more oxygen on the metal
surface.