Corrosionofmetals

MB JASS09 FlaviusDeleanu KathrinLorenz ChristinaEngelhardt

Outline
corrosion of metals in aqueous solutions corrosion processes (material, biomaterial, current density potential diagram) Pourbaix-diagram Pourbaix diagram different types of corrosion surface corrosion pitting corrosion corrosion of metals titanium ion 316L magnesium Stents ion magnesium

Corrosion
Whatiscorrosion? Definition(DIN50900): Reaction ofamaterial withtheenvironment Measurablechange (properties,behavior) Probablydamage ofafunctionorsystem Appearance: Basicallyelectrochemical

Corrosion
Genericchemicalformulaforanodic metalloss: M M+ +e (Oxidation)

Theproducedelectrons areconsumed atthecathodic side: 2possibilitiesinaqueoussolution: I) II) 2H+ +2e H2 (Reduction)

O2 +2H2O+4e 4OH (Reduction)

Corrosion
Corrosionofiron (Fe):

Corrosion

Anode:Fe Fe2+ +2e Cathode:O2+4e +2H2O 4OH Formationofrust:Fe2+ +2OH Fe(OH)2

Corrosion
Onlynoblemetals arestable inaqueousenvironment Oxidationp potential>Reductionp potential (noblemetal)(environmentalspecies)

Otherreasonforstability: PASSIVITY:stablenondissolvableoxidelayer on thesurface primarilytitanium!

Corrosion

:noblemetals,cathode :b basemetals, l anode d

U=Eanode Ecathode <0 reactionpossible!
Actuallytitanium islessnoble, but:highO2affinity:formationofa protectiveoxidelayer

Corrosion

Correlation:CurrentFlowandWeightLoss Metallossisproportionaltotheproducedelectrons Metallossisproportionaltothecurrentflow Corrosionratescanbedeterminedbyapplying current(j)againstpotential(E)

Corrosion
Measurementofj/Ecurve: Voltagesettingbetween corrodingelectrodeand referenceelectrode Current between corrodingelectrode and counterelectrode Thereferenceelectrode keepsitspotential (highohmicinput)

Corrosion
log(currentdensityj)
critical current d density
evolutionofoxygen

jcrit

active dissolution

anodicreaction
passivecurrentdensity

evolution ofO2

passive current density jpass evolutionofH2

cathodicreaction

potentialE (~time; againstreference electrode)

Corrosion Pourbaix-diagram
pHvalue ofblood

Pourbaix diagram: electrochemicalequilibrium q diagram validonlyforendlesstime! noinformationabout reactionrate!

Corrosion Pourbaix-diagram

Fe Fe 2e
0 E Fe / Fe E Fe / Fe

0,059 lg c Fe 2

E Fe / Fe 0,62Volt
NopHvaluedepandance:horizontallineI

Corrosion Pourbaix-diagram

2 Fe 3H 2O Fe2O3 6 H 2e

E Fe / Fe 2O3 E

0 Fe / Fe 2O3

c6 0,059 lg 2H c Fe 2

E Fe / Fe 2O3 1,09 0,18 pH

pHvaluedepandance:lineII

Corrosion Pourbaix-diagram

2 Fe 3H 2O Fe2O3 6 H

c6 H c
2 Fe

K 101,45

pH 1,76

purechemicalreaction:vertical lineIII

Corrosion Pourbaix-diagram
Yellow:inertarea

Corrosion Pourbaix-diagram
Yellow:corrosionarea

Corrosion Pourbaix-diagram
Yellow:areaswithstableoxides

Corrosion
Corrosionofimplantsinhumanbody: Blood=complexelectrolyte *pH=7,4(0,05) generatedwithabuffersystem *bloodconsistsofcellsandplasma (proteinsand electrolyteslikeCl orPO43 dissolvedinwater) moreaggressivethanseawater! Corrosionincreasedatareaswithmechanicalstress Canprovokeaninflammation

Corrosion
Howdometallicionsdamagethetissue?

I)Ph valueandtheoxygenpartialpressurecandiversifyand thiscanchangethechemicalenvironment (metalionsformheavilysolvablecompounds)

II)Metallicionscanchangethecellmetabolism

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Different types of corrosion

corrosion
surface corrosion atmospheric corrosion galvanic (contact) corrosion

types of local corrosion

pitting corrosion crevice corrosion stress-cracking corrosion intercrystalline corrosion

Surface corrosion

Fe Fe

mechanism: Mechanismus

2e

2 H 2e H 2 O2 2H 2O 4 e 4 OH
preconditions:

acid medium alcaline medium

- conductive surrounding (even a very thin water film is enough) - homogeneity of surrounding & material ! anodic and cathodic reactions are parallel !

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Galvanic corrosion
dissimilarconductingmaterialsareconnectedelectricallyandexposedtoanelectrolyte

electrolyte

preconditions: electrochemicallydissimilarmetals metalsareinelectricalcontact metalsareexposedtoanelectrolyte

morenoble

lessnoble

metalsinelectrolyte differentcorrosionpotentialsofdifferentmetals potentialdifference=drivingforceforgalvaniccurrentflow lessnoblematerial morenoblematerial =anode =cathode accelerationofcorrosion reductionofcorrosion

Pitting corrosion
Kathodicreactionattheperipheryofthedrop PassivationofborderareabyincreasingpH Lowp pH&lowO2concentrationinthemiddle dissolving gofion aroundanodicarea:formationofrust

O2 2H 2O 4 e 4OH Fe 2OH Fe(OH ) 2 4 Fe(OH ) 2 O2 4 FeO(OH ) 2 H 2O

Corrosion withO2 concentration

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Pittingcorrosion
Initiation: Oxidelayer breakup

Processesin thepit pittingcorrosionon surfaceofcastironbathtub

FeCl2 +H2O>FeClOH+H+ +Cl

[23] [24]

Influences on corrosion

- pH - microstructure i t t - temperature - O2-concentration - velocity of flow - salt-concentration lt t ti

Porbaix-diagram galvanic l i elements l t diffusion constant O2-conc. in open systems drop-model

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Corrosion of metals
Examples: titanium iron 316L magnesium

Titanium

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Implants

Eigenschaften properties
3)3 density (g/cm Dichte (g/cm )

Knochen bone 1,8-2,1

Magnesium magnesium 1,74-2,0

Ti TiLeg. alloy 4,4-4,5

Co-Cr CoCrLeg. alloy Edelstahl 316L 8,3-9,2 7,9-8,1

Youngs modulus E-Modul (GPa) (GPa)

g Bruchzhigkeit fracture toughness (MPam1/2 ) 1/2 (MPam )

3-20

41-45

110-117

230

190 73-117

3 6 3-6

15 40 15-40

55 115 55-115

07 0,7

Titanium

rutil

anatas

brookit

structures melt

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Titanium

CorrosionResistance?

Titanium
Ti:creationofatitaniumoxidelayer goodcorrosionresistance Ti Ti3+ +3H2O Ti2+ +2e TiO2+ +2H3O+ +e 1.75V +0.10V

TiO2 ntype yp semiconductor, ,Egap g p3.1eV amorphous anodisation:crystalline(athigherpotentialsortemperatures)

=underspecificelectrochemicalconditions:specificsurfacemorphology

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Passivation of Titanium

titaniumoxidelayerTiO2 highlystablesurfaceoxidelayerprovides excellentcorrosionresistance

Titanium - applications

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Iron

Iron (Fe)
4,7wt.%ofearthcrust Resistant indryair,indryCl, concentratedsulforicacidand inalkalinemedium(except NaOH)withpH>9

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Iron (Fe)

The more active metal in the galvanic couple becomes the anode and gets oxidized. The noble metal is the cathode.

316L

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316 L
Surgicalstainlesssteelisanspecifictypeofstainlesssteel,used inmedicalapplications

Elementalcomposition
Wt.%

Low content of C High addition of Cr and Ni

316 L

Corrosion Resistance ?

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316 L

Formationof acompact oxide layer (Cr2O3) protection against corrosion

but Thermaltreatments (welding,annealing)lead to Cr23C6 precipitationsinthe grain boundaries 23Cr +6C Cr23C6 Insidethe grain decreased Crconcentration

316 L
Cr23C6 precipitations

Crcontentbefore treatment

Crprecipitationsatthegrainboundaries LessCrnearthe h grainboundaries b d

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316 L
Cr23C6precipitations

Afterthermaltreatment: highCrcontentatgrain boundaries Crcontentbefore treatment Aftertreatment

LessCrnearthegrainboundaries Criticalp passivation currentdensity yincreases Possibilitytolosepassivation

316 L
Cr23C6precipitations

Afterthermaltreatment: highCrcontentatgrain boundaries Crcontentbefore treatment Aftertreatment

Differentconcentrations neartheg grainboundariesand inthegrainboundaries Dangerofcontactcorrosion

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Current density potential diagram

currentdensityj
evolutionofoxygen

jcrit
active passiveevolution ofoxygen currentdensity jpass dissolution

potentialE
counter electrode reference electrode

Measurement:electrochemical cellwith3electrodes
working electrode

j/Ecurves

316L Ti

Electrolyte:0,14MNaCl,pretreatment:grinding(1200)

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316L
mainlyprotection but pitting causedby chlorideions
Microscopicpictureof316Lafter electrochemicaltreatment

Titanium

Leveling L li of fgrinding i di groovesbecauseof grownoxidelayer

MicroscopicimageofTiafter electrochemicaltreatment

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Magnesium

Implants

Eigenschaften properties
3)3 density (g/cm Dichte (g/cm )

Knochen bone 1,8-2,1

Magnesium magnesium 1,74-2,0

Ti TiLeg. alloy 4,4-4,5

Co-Cr CoCrLeg. alloy Edelstahl 316L 8,3-9,2 7,9-8,1

Youngs modulus E-Modul (GPa) (GPa)

g Bruchzhigkeit fracture toughness (MPam1/2 ) (MPam1/2 )

3-20

41-45

110-117

230

190 73-117

3 6 3-6

15 40 15-40

55 115 55-115

07 0,7

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Magnesium

Hexagonalclosedpacked magnesium 1.74g/cm3

atomicnumber atomicmass symbol name boilingtemperature meltingpoint

Magnesium

CorrosionResistance?

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Magnesium
Mg: highlynegativeelectrochemicalpotentialof2.38V lowcorrosionresistance
redoxseries

MgO: noformationofprotectionlayer
WHY? differenceinmolarvolumeofMg&MgO flakingoff causedbytensile&compressionstresses Mg corrosioneveninwater Mginacids highestcorrosion increaseofcorrosionrateby impuritiesinMg especiallyFe,Ni,Cu galvaniccorrosion

Magnesium
corrosionreactionsofmagnesium

M.P.Staigeretal./Biomaterials27 (2006)17281734

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Magnesium-corrosion

local corrosion of passive layer by Cl rapid increase of corrosion rate pitting corrosion

Na+ Blut [mmol/l] 142,0

K+ 3,6-5,5

Mg++ 1,0

Cl95,0-107,0

Pourbaix-diagram of Mg

Passivation

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Magnesium

Mgcorrosioninthebody?

Magnesium corrosion in the body?

Simulatedbodyfluid

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Magnesium corrosion in the body

EDXanalysis: degradedimplant:replaced byaconversionlayer containingmainlyCa&P rareearthelementswere distributedhomogeneously inthecorrosionlayer&in theremainingimplant materialbutnotinthe surroundingbone

Biomaterials26(2005)35573563

Magnesium corrosion in the body

Subcutaneousg gasbubbles observedonpostoperative radiographsfor4weeks duringmagnesiumimplant degradation

Biomaterials26(2005)35573563

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Oxidelayers specificvolume
PBRatio<1
Mg Al

PBRatio=12

Fe

PBRatio>2

nM+mO2 =MnO2m

Stents

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Bioabsorbable stents

PossibleMaterials??

Bioabsorbableironstents

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Bioabsorbable Iron Stent

Ironisanessentialelement(dailyneed:0,55mg) stentweighsabout40mg(coronary)or250mg (peripheral) lowtoxicity,becauseofthelowrateofcorrosion systemictoxicityisnottobeanticipatedeven afterimplantationofmultiplestents

Bioabsorbable Iron Stent

Studieswithpureiron(lessthan1%contamination)foils (diameter26mm,thickness0,91mm)inelectrolyte:

Loss of15%massafter1weeks incubationinhumanserum

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Bioabsorbable Iron Stent

Invivostudies

12monthsafterimplantation:corrodible ironstent (left)and316Lstent(right)in thedescendingaortoofaminipig

Bioabsorbable Iron Stent

Macroscopicaspectofcorrosionprocess3(a),6(b)and12(c) monthsafterimplantation

(a) Strutsofthestentsareclearlyvisible,corrosionplagueslimitedto theintersections (b) Progressivelossofstructure,accumulationofcorrosionproducts (c) Lossofintegrity

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Biodegradablemagnesiumstents

ReasonsforfavoringMgasstentmaterial
Hypothromboticproperties

Predictabletissuetolerance Mechanicalproperties:Outstandingstabilitytomassratio Therapeuticallyused Vasodilatingproperties: Asaphysiologiccalciumantagonist, antagonist magnesiuminhibitsthemusclecontraction andthusthetoneofvessels.

[]

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Bioabsorbable magnesium-stent
1stent(1.1mm 10mm): 4 mgmagnesium 0.7ldrinkingwater: 110mgmagnesium

Mg essentialmineral: 20ginhumanbodies 350mgrecommendedingestionperday Mg relaxationofmuscels Mg verylowallergenreactions

DegradationofMgstents
Mgalloy remainingMgalloy

conversionlayer after14days

after56days

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Thank you for your attention!

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