Aspects of localized corrosion: - pitting - galvanic - crevice

Combination: Pitting Galvanic corrosion

Stainless Steel: conducting passive film Anodic reaction: in the pit Cathodic reaction: on the passive film + in the pit Cathodic area is much larger than anodic area
(cathodic reaction in the pit can be neglected)
Active Pits

Galvanic coupling induces fast localized attack

Intact semiconducting Passive layer

Stainless steel
2

Aluminum alloys: insulating passive film Anodic reaction: in the pit Cathodic reaction: in the pit (or on intermetallic phases) No reactions on passive film External galvanic coupling with intermetallics can induce fast localized attack

Active Pits

Intact insulating passive layer

Aluminum
3

Are all the passive oxide conducting ?

Photoelectrochemistry allows to answer this question
Monochromatic light of different energies (wavelength) is shined on the material surface under electrochemical control The additional current as function of the light energy is recorded

Experimental setup

Charge injection at semiconducting surface

At an oxide-solution interface, an equilibrium between the redox potential of the reduction reaction and the Fermi level of the oxide is established
W: space charge domain

When the surface is sufficiently polarized or light is shining on the surface, electrons can be promoted in the conduction band
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Emitted Photocurrent from a passive film

The fundamental model concerning the description of photoelectrochemical effect in a bulk semiconductor has been derived by W. Grtner.

- W e Iph = q 11+ L
with : : L: W: Incoming light intensity Absorption coefficient Diffusion length of the charge carriers Space charge domain width

Obviously not all the incoming photons can successfully be converted in electron-hole pairs, the Quantum efficiency h of a process can be formulated:

Iph h N el = = Nphot q
Nel = Number of generated electrons Nphot = Number of generated electrons
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Emitted Photocurrent from a passive film II

The wavelength dependence of the photocurrent and the band gap Eg determination

h - Eg =A h
-

with h = hc/

For very thin semiconducting film the exponential term can be developed in a TaylorSeries

Iph resp. h
For a constant incoming light wavelength, the Grtner theory provides a direct relation between the electrochemically applied potential and the photocurrent (Ufb: flat band potential)

Iph = q W

W = (U-Ufb)1/2

Some example of passive surfaces

- Thin Ti passive oxides are semiconducting (band gap: 3eV ) - Thin passive Ni oxides are isolating
Titanium oxide Maximal photocurrent Insulating Ni oxide

1.4x10

-4

1.4x10 Photostrom [A] (A) Photocurrent

-4

Photocurrent (A) Photostrom [A]

1.2 1.0 0.8 0.6 0.4 0.2 0.0 250

1.2 1.0 0.8 0.6 0.4 0.2 0.0 250

Band gap energy

Wavelength (nm)

300 350 400 W ellenlnge [nm ]

450

300

350 400 450 W ellenlnge (nm) [nm ] Wavelength

500

Surface functionalizing with TiO2 nanoparticles

Environmental interactions: cleaning and bactericide effects

TiO2 TiO2

TiO2 TiO2

TiO2 TiO2

TiO2 TiO2

TiO2 TiO2

Metal - Matrix with TiO2Nanoparticles Substrate

Photo-activity of TiO2 in metallic matrix

0.5

0.40 mA

0.1 M Na2SO4 solution

Photocurrent Intensity [mA] Photostrom-Intensitt [mA]

0.4
abgeschiedene Nickelschicht Ni electro-deposition

0.3

0.15 mA
0.2 0.1

Abscheidung mit Titandioxid Ni+ TiO2 (agglomerated) verbesserter Abscheidungsprozess Ni + TiO2 (dispersed)

Band gap energy 0.01 mA

0.0 250 300 350 400 450

Light wavelength [nm] Wellenlnge des Lichts [nm]

- Pure Ni (with surface oxide) does not show photoelectrochemical effects

- Very important photoelectrochemical effect is obtained upon integration of TiO2 nanoparticles (intensity smaller for agglomerated particles)

10

Semiconducting behavior of passive Steel

All the stainless steels have semiconducting surface oxides The properties are changing with Mo addition

Solution: 1M Na2SO4 300 mV SCE

11

Type of steel
CrNi steels

Corrosion Abbreviated name resistance class*) I X5CrNi18-10

X4CrNi18-12 X6CrNiTi18-10 X2CrNi19-10 II X5CrNiMo17-12-2 X6CrNiMoTi17-12-2 X2CrNiMo17-12-2 X3CrNiMo17-13-3 X2CrNiMo18-14-3 X2CrNiMoN17-11-2 X2CrNiMoN17-13-3 X2NiCrMoCu25-20-5 X2CrNiMoN17-13-5 X2CrNiMoN22-5-3 IV

Material PREn**) no.

1.4301 1.4303 1.4541 1.4306 1.4401 1.4571 1.4404 1.4436 1.4435 1.4406 1.4429 1.4539 1.4439 18 18 18 19 24 24 24 26 27 30 32 35 37

Applications
humid areas

CrNiMo steels

mild outdoor climate, weathered

III

1.4462** 37 *) 47 48 50 (66) (68) (69)

outdoor climate, unweathered industrial atmosphere, weathered

X1NiCrMoCuN25-20-7 1.4529 X1CrNiMoCuN20-18-7 1.4547 X2CrNiMnMoNbN25- 1.4565 18-5-4 NiCr21Mo14W NiMo16Cr15W NiMo16Cr16Ti 2.4602 2.4819 2.4610

aggressive media indoor swimming pools, tunnels, sewage treatment plants Combination of aggressive media chemicals industry

Special materials

Oxides and pitting susceptibility

When the potential of the sample surface is modified due to a polarization, the charge in the space charge layer can also be switched a) Adsorption of Cl impossible b) Adsorption of Cl- favorable

Amount of metastable pits is influenced by this parameter

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Mg AZ alloys and microstructure obtained

Nominal composition:
Mg: Al: Zn: Mn: Ni: Fe. balance 7 % (6.91% from ICP-AES) 1 % (0.84%) 0.11 % 0.001 % <0.004 %
200m

AZ71
as cast

Multiple phases alloy:

Primary Mg phase (2-3% Al) Eutectic phase (richer in Al) Intermetallic Mg17Al12 phase Intermetallic Al8Mn5 phase

Sample preparation
100m

T4
420C/30h 14

- NRC as cast - Wet polishing to a 1200 grit finish in water

Mg oxides and influence of Al in 0.01 M NaOH

200x10 Photocurrent normalized (A)
-6 Mg 99.95% pure Directly after im. + 1 hour + 3 hours + 3 days

150

100

50

0 200
-6

300

400

500

Wavelength (nm)

200x10 Photocurrent normalized (A)

- Large photocurrent intensities can be obtained for pure Mg and semi-conducting properties of the hydroxide formed can be investigated - For the alloy, the presence of Aluminum in the surface hydroxide suppresses the photoelectrochemical current. - Al hydroxide is insulating

150

AZ 71 NRC T4 Directly after Im. + 1 hour + 3 hours + 3 days

100

50

0 200

300

400

500

Wavelength (nm)

15

Summary
Most of the passive surface layers (hydroxide or oxides) are semiconductors. This is the case for Ti oxide (very good catalyst), Fe, Cr, Mg (when it is stable) They all have a small band gap energy (2-3 eV) and galvanic coupling of the intact passive layer with active pits is an important factor There are some examples of insulating hydroxides: Al , Ni These passive layers are not having a galvanic coupling influence

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Crevice corrosion: observation

A locally increase of corrosion attack in an existing geometrical feature (recess, hole, scratch, crack, joining area, welding area) The whole crevice surface is attacked but quite often the bottom region are more damaged

Due to the corrosive attack, the crevice is widened possibly until breaking of the part (often solution leakage)
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Examples: macro and micro-crevice

Microscopic crevice are the result of dissolution of defects like the MnS example Macroscopic crevice corrosion are often at the joining of tubes or weld

Initial state
Passivefilm

Dissolution of MnS
Mn2+ S spezies

Formation of Passivefilm on top of MnS

Precipitation of Mn Oxide(s) and pushout of part of MnS

MnS

MnS

MnS

Mn2+
MnS

S spezies

SS

SS

SS

SS

Crevice corrosion susceptibility of corrosion resistant passive materials is always higher than pitting corrosion because the unfavorable geometry is already present 18

Mechanisms (see analogy with pitting)

1) Crevice corrosion is the result of an active-passive element - The crevice (geometrical recess) is active - The material surface is passive
a) Stagnant solution or dirt particles adsorbing Cl- anions dor example are increasing locally the Cl- concentration b) High chloride contents are reached inducing pitting c) Hydrolysis of the corrosion products induces pH drop d) Autocatalytic mechanism
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A lot of crevices in riveted structured(macroscale)

Example: Airplane structure Different areas at the bottom of the planes are at location where condensation takes place and subjected to crevice corrosion

White areas: mostly dry Red areas: often humid

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Complex crevice corrosion problems

Corrosion found at fasteners holes and joints Here, not only crevice are present, but screws (steel) and structures (Al alloy) are made of dissimilar materials !

Crevice + galvanic corrosion is possible

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Other example of crevice corrosion (microscale)

For Stainless Steel

Poor quality of soldering or welding processes

0.1M NaCl solution

Electrochemical cell with O-rings

Crevice corrosion Pitting
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Crevice corrosion and coatings DLC

Diamond-like Carbon (DLC) coatings are ideal for applications where low friction is aimed at Deposition by PA-CVD from C2H2 gas Commercial applications:

DLC coated hard disk, diesel compression cam plate and injector

Properties of DLC 1500-3500 HV temperature stability < 350 C very low friction and wear stable against acids and alkaline media biocompatible, haemocompatible

DLC coated screw compressor, wrist pin and gear

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Failure of coated medical implants

Its not the coating which is bad, its the interface that needs to be analyzed

Adhesion/delamination in corrosive media ?

DLC

interlayer CoCrMo or TiAlV

BUECHEL-PAPPAS HIP REPLACEMENT SYSTEM

cracks
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DLC coating local failure in-vivo (in patients)

101 patients DLC/Polyethylene(PE) 101 patients Al2O3/PE 8.5 year fallow-up 50% of DLC/PE failed

2 m DLC 2 m DLC-Si gradient ca. 60 nm Si Ti-Al-V

Retrieved DLC-head: Numerous pits revealing the metallic substrate, severe PE wear
G. Taeger et al., Mat.-wiss. u. Werkstofftech. 34 (2003) 1094

Multilayered structure determined by XPS depth profiling

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Focused Ion Beam section on defect

Overview: Left picture: Right picture: A crack at the right end of the delamination has been followed Enlargement, several cuts needed to find the end of the delamination crack.
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During cutting a part of DLC delaminated (right picture).

Detail of the crevice corrosion attack (nanoscale)

Silicon Pourbaix Diagram

DLC-Si Si TiAlV

- The first 50 nm above the TiAlV substrate are more or less totally corroded away (the smooth round shape of the corroding tip indicate that it is not a crack growth) - Silicon is not stable in vivo due to crevice corrosion and the related local aggressive media that can be established. It is important to note that this very well known phenomenon is not predictable by simple thermodynamic consideration !
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Artificial crevice setup

In order to investigate the corrosion mechanisms in pits and crevices, it is possible to use a model experimental setup called artificial crevice.

Front View

Side View

It is a plate (foil) of the material of interest (thickness: t, width: w) pressed between two transparent plastic sheets This crevice (depth ) is connected to an electrochemical system (working electrode)

Plastic sheet

Al alloy sheet t w

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Potential evolution in crevice

The total potential drop between the reference electrode and the bottom of the crevice can be formulated by
Ref. electrode

E tot = E r + E s + E iR
r tot: r:
Plastic

R
total potential drop potential difference between reference electrode and non corroding surface surface overpotential ohmic potential drop Plastic

Ref. electrode

depth

Metal

i
width
Metal Plastic
29

Plastic

s: iR:

The different potentials in detail

The surface overpotential is simply given by the Butler Volmer relation

E s = log(ia / io )
The iR drop contribution is given by the ohms law

EiR = inet R
The measurable potential difference can be then expressed in terms of all the parameters

Etot = A + log(inet / 0.85) + inet R

A = E r log(io )
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Experimental investigation: example of Aluminum

It is not possible to measure all the components of the potential individually But if the net current can be determined, then the d ifferent components can be discussed
10 Current Density (A/cm )
1 0

0.2 Cu 0.022 Cu

The following procedure is used. Apply a certain potential. In this case, it was started at 0V SCE and the potential was gradually decreased The dissolution rate can be measured optically through the transparent walls

10 10 10 10 10 10 10

-1

-2

99.99 Al

Al - 3.9 Cu Al - 1.9 Cu

-3

-4

-5

-6

-1

-0.8

-0.6 -0.4 -0.2 Potential V (SCE)

0
31

0.2

The potential evolution: part II

The dissolution current is related to the dissolve d depth through the total charge Qano:

Qano = wt 0 nF / M

o is the dissolved depth for a given condition

Current Density (A/cm )
2

The measured charge is different

1.2 1

Data

0.2 Cu

Qnet = Qano Qcath

Because of the cathodic Reaction occuring in the crevice

Al

0.8
3.9 Cu

0.6 0.4 0.2 0 -2 -1.5 -1 -0.5 0 0.5 1 Potential V (SCE) 1.5 32

1.9 Cu 0.02 Cu

iR

Q net = 0 .85 Q ano

Avoid macroscopic crevice corrosion

The same precautions as for pitting corrosion are applicable Avoid the presence of deposits, dirt, lime Conception mistakesavoid deep and narrow recesses as well areas with stagnant solution
To avoid Optimized process !

Crevice in welds solution

Welded from both sides solution

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