Passivation

generates corrosion protection of most of metals and alloys used in industrial applications ?

What happens with iron as a function of the pH

In acidic solutions
strong anodic metal dissolution

In neutral solutions
formation of a thick, porous, hydroxide layer with poor adhesion properties and limited corrosion protection effect

In alkaline solutions (pH > 10)

formation of thin (1-2 nm), adhering Oxi/hydroxide layer that protects the surface from corrosion

Passive layer

Example: Pourbaix diagram of iron in water

Fundamental aspects of passivation

A passivation reaction requires:

Metal oxidation to provide the necessary cations for the formation of an oxide layer Water and removal of protons to provide the hydroxyl or oxide anions

Passivation will be much more likely to occur on metals with low redox potential (active metals) because of the high oxidation susceptibility and the dissolution current available 4

Factors improving the ability to obtain passivation:

Water content
Obviously, a certain water amount in a solution is necessary to provide through splitting enough OH- or O2-

pH of the electrolyte
High pH provides large amount of dissociated OH- cations. The first step of the deprotonation process already occurred and passivation is accelerated

O2 amount
Reduction of gaseous oxygen also produces OH- and therefore passivation can be promoted this way
5

How is a passive behavior evidenced ?

With an electrochemical polarization curve (anodic part is relevant)
Active Metal Passive Metal

How is a passive behavior evidenced ?

log I active passive Transpassive dissolution Or Water dissociation

ER,a

Epass

Eact

Ed

On an anodic polarization curve Active domain very rapid current increase (charge transfer controlled) order of magnitude decrease of current
7

Transition active passive domain Passive domain

current in the microampre/cm2 domain , stable surface

Important parameters

Log I ac tiv e

Icrit

passive Transpassive dissolution Or Water dissociation

ER,a

Epass

Eact

Ed

Passivation potential Epass : potential where passivation can take place

Icrit: maximal current density reached in the active state and inducing passivity
Passive current ip: indication of the stability of the surface (usually 10-6 Acm-2) Passivity domain: between Epass and Ed : it has to be very large to insure protection of
a metal Depassivation potential (Ed) can be of different nature Current increase can also simply be dissociation of water
8

Some typical cathodic partial reactions

Cathodic reaction

Most frequent passivation situations

Supported by the cathodic reactions
In acids:

In neutral and alkaline solution:

For the anodic reaction in the passive domain, following reaction:

in the potential domain where a stable oxide film can form on a metal surface
10

Passivation in acidic solution

Equilibrium of anodic current with hydrogen reduction At the corrosion potential:
We can distinguish 3 important cases

|Ianodic| = |Icathodic|

a) Spontaneous and stable passivation

Icorr= Ip
E

Ecorr

11

b) Unstable passivity with multiple possible corrosion rates

Icorr= Ip Ecorr
E

Ecorr

Situation 1: if the surface is passive, the surface oxide can maintain its stability Situation 2: instability of the surface Situation 3: if the surface oxide is removed, no stabilization is possible
12

c) no passivation possible
Icorr= Iactive

Ecorr

The presence of a stable passive film can depend of very small subtle changes
13

Passivation in neutral and alkaline solutions

Equilibrium of anodic current with oxygen reaction At the corrosion potential:

|Ianodic| = |IO2,D|

The diffusion limited current density is the main factor deciding if a system can achieve stable passivity
Icorr= Iactive

a)Two equilibrium potentials are possible

Ecorr

Icorr= Ip
E

Ecorr

14

b) Increasing the oxygen concentration

Icorr= Iactive

Icorr= Ip Ecorr
E

Ecorr

In case a) and b) two equilibrium states are still possible

Passivity is only possible if the material is already passive Usually the material is actively corroding
15

c) very high limiting current When the oxygen content of the solution is high or the diffusion layer thin because of forced convection conditions

Icorr= Ip
E

Ecorr

only |ianodic| = |iO2,D| in the passive domain is possible as a result, very small corrosion rate are obtained
16

Natural passivation curve measured on Nickel

Example of chemical passivation obtained by varying the cathodic reaction present in the system

Continuous line: measured curves in 2M H2SO4 Different dots: measured corrosion current density and corrosion potential for different redox solution

Current density i

Electrode potential E

17

Identify your environment !

Stability of the surface is not only a characteristic of the anodic reaction

Active or Passive behavior It is important to know the cathodic reaction evolution of the species present in solution

Current density i

Different oxidizing agent can result in

Electrode potential E

18

Passivity: passive oxide film

how to investigate this important phenomenon that allows corrosion protection of important metals and alloys ?

19

20

Important features of passive surfaces

1) When do we really have a passive film on the surface ? Detailed electrochemical investigation 2) Why is the surface becoming so stable ? presence of a very thin and stable oxide Oxide film composition X-Ray Photoelectron Spectroscopy
3) Why is the surface still vulnerable ?

dynamic formation and dissolution of oxide Oxide film stability Electrochemical Quartz Nanobalance

4) What kind of cathodic reaction can take place on a passive surface ? Semiconducting vs. insulating oxides Photoelectrochemistry
21

Passivation of iron in acids ?

Particularity:

Passivation of Iron: Examples

Current Density i

- Very high critical currents - Broad active domain inducing large amount of dissolved iron ions - Sudden drop in current

Polarisation Potential E

Suspicion of the presence on the surface of thick corrosion products

22

When we do not speak of passivation !

Typically in the case of iron in acids, the surface is partially protected by deposition of corrosion products due to saturation effects. The best way of evidencing this effect is to increase the diffusion rate of the dissolved ions by using a rotating disc electrode Rotation speed (rad/s)

23

Rotating disc electrode

Reference electrode Rotating disc Counter electrode

24

Rotating disc electrode II

Levich Equation

Electrode

i L = 0.62 n F c0 D 3

2
Resin

c0: D:

concentration diffusion constant viscosity Rotation speed

Laminar flow
25

=2 f:

Resin

Necessity of water for passivation

Example of Iron in an acetic acid/ sodium acetate solution

- With different addition of water

No formation of oxide films an absence of water. Oxygen reduction is not sufficient to form a passive film
26

Example of the formation of thick corrosion products: Zn

Current Density i

Potentiodynamic polarization curves in 1M KOH:

Zink in KOH Lsungen - In this very alkaline solution,

formation of metallic hydroxide is very likely but does not guarantee a adequate corrosion protection
Polarisation Potential E

Current Density i

Polarisation Potential E 27

Example of very stable passivity: Titanium

Current Density i

Polarisation Potential E

In the case of titanium, the pH domain for active dissolution is very small - Also very small critical current densities (lower than 1 A/cm2) even in very acidic condition. Such a material is considered to show extremely stable passivation
28

Passivation of Cr Ni Steels
Addition of Cr changes completely the passivation behavior of steel: - Critical current density decreases (very positive effect) - Shape of the passivation curves changes from sudden drop (low alloyed steel) to a smooth transition characteristic for stable passive film growth (thermodynamic stable compound)

Current Density i

Polarisation Potential E

29

Passive film formed on Fe25Cr

What happens during passivation of Fe25Cr ? In acidic solution: In 0.1M H2SO4 + 0.4M Na2SO4 Passivation potential: 0.5V SHE

In water In alkaline 0.1 M NaOH solution For alloys, passivation studies are linked to surface analytical characterization
30

Principle of X-Ray Photoelectron / Auger Spectroscopy

Analysed electrons come from the first few nanometer of the surface - Ideal for the
characterization of thin oxides layers - AES with focussed electron beam (good lateral resolution) - XPS poorer lateral resolution because but easier access to chemical information
31

Interaction of a photon / electron with electrons of the atoms

Inelastic mean free path as a function of electron energy

Electron energy is element specific

32

Where is the chemical information ?

- Oxidation state can be characterized by energy shifts because of the different amount of electrons surrounding an atom in ions - Oxides and hydroxide can be very well distinguished because the influence of the proton (H+) on O2- energy level is stronger than the influence of the surrounding metallic ions.
4000

A)

O 1s

Intensity [counts/s]

3000 O
2-

2000

0H

1000 SO 4 0 528 530 532 Binding Energy [eV] 534

2-

H2 O

33

XPS peak parameters for different important elements

- For stainless steel: O, Cr, Fe are the constitutive elements of the passive film

Mo is also used to obtain higher corrosion resistance

34

XPS Spectra of chromium 2p level

2500 2000 Intensity [counts/s] 1500 1000 Cr 500 Cr met 0 572 Cr other
3+

A)

Cr 2p 3/2

Fe25Cr alloy passivated at 0.5V SHE during 5 minutes (solution: 0.1M H2SO4 + 0.4M Na2SO4).

Cr hyd

2000

Cr 2p

576 580 Binding Energy [eV]

1500 Intensity [counts/s]

1000

Cr hyd

500 Cr met

Cr

3+

Detail of the 2p3/2 peak as a function of the X-Ray source used: a) Al k monochromatized, pass energy 5.85 eV b) Al k standard, pass energy 5.85 eV
3000

Cr other 0 575

B)

Cr 2p 3/2

satellite
Intensity [counts/s]

2500

580 585 Binding Energy [eV]

590

2000 1500 Cr hyd 1000 500 Cr met 0 572 576 580 Binding Energy [eV] Cr other Cr
3+

Chromium 3+ in oxide and hydroxide form is found in the film

35

Sputter depth profiling for thick oxides

Sputter profile = raster with focused Ar ion beam

Analysis of the surface in the crater

analyzed thickness ~ 5 nm
36

Example of passive layer on steel in different media

- Completely different oxides in contact with a solution
12x10
3

14x10 Feox Cr ox O
2-

10

12 10

Feox Cr ox O
2-

OH

OH

Intensity

Intensity

8 6 4 2 0

0.0

0.5

1.0

1.5

2.0

2.5

3.0

0.0

0.5

1.0

1.5

2.0

2.5

3.0

Sputter depth [nm]

Sputter depth [nm]

Distribution of the main anions and cations in the passive film formed on the surface of a Fe25Cr alloy after polishing.

Main anions and cations in the passive film formed on a Fe25Cr alloy passivated at 0.5V SHE during 1 hour in 0.1M H2SO4 + 0.4M Na2SO4.
37

XPS spectra of iron 2p level

Fe25Cr alloy passivated in 0.1 M NaOH at 0.5V SHE during 1h. Fe25Cr alloy passivated in 0.1 M NaOH at 0.5V SHE: inner oxide (sputtered during 5 minutes)
Fe 2p
1500
1000

1200

Fe 2p

Intensity [counts/s]

800
3+

Intensity [counts/s]

1000 Fe
2+

600 Femet 400

2+

Fe

Fe 200

500 Fe
3+

FeOOH

satellite

satellite
satellite

satellite
0 705 710 715 720 725 730 735

0 705 710 715 720 725 730 735

Binding Energy [eV]

Binding Energy [eV]

The iron ions on the surface are more in the 3+ state The internal part is more Fe2+ state
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Influence of chromium, Nickel, Molybdenum

- Chromium is the important element to build a stable passive film (an amount of 12% is necessary for significant enrichment in the passive layer) - Ni and Mo are almost not present in the passive oxide film

Cr content in alloy

Metal

Oxide

Electrolyte
39

How to measure passive film growth and dissolution

One possible answer: from a mass change It is then possible to relate the mass to the thickness d= M/ (A )
d: M: A: : thickness mass electrode area density

How to be extremely accurate ? use the frequency change of a piezoelectric crystal to record thickness changes

40

Quartz crystal nanobalance: principle

Quartz electrode

q q

q q

f f

f = vtr / 2dq
Vtr: speed of transversal elastic wave dq : total thickness of the quartz crystal
41

42

Frequency variation in case of a thickness change

df / f = d(dq) / dq df / f = dmq / (q A dq) = dm / (q A d) df = - f2 / (A q0.5 q0.5) dm
Limitation: - relation valid only for thin electrode on the quartz (2% of the quartz mass) - a good adhesion between the electrode and the quartz is necessary For 10 MHz the resolution obtained is For iron, chromium this means: 1.76 ng/Hz 0.02 monolayers
43

Electrode in solution
Metal Oxide Solution
Electrical contacts

Thickness: 2 nm

Variable pressure in the glass tube

Electrolyte level

Silicone
Quartz plate

Thin Electrode on quartz plate

Electrical contact

The mass charge relation

The most simple case is the Faraday relation: F n Mj :Faraday constant :reaction valency :molar mass of the species involved in the reaction

dm M j = i dt n F

45

Calibration on a well defined system

Solution : 10-2 M CuSO4 Deposition potential : - 0.25 V SHE Dissolution potential: 0.5 V SHE Linear mass increase in the low potential domain
6000 ]
2

Well defined mass change / current density ratio

1.2
-0.2
s mA] current density (dm/dt)/i

Current density (mA/cm2)

2) Mass change (ng/cm mass change m [ng/cm

5000 4000 3000 2000 1000 0 0 20 40 time [s] 60

1.0 -0.3 0.8 0.6 -0.4 0.4 0.2 -0.5 0.0 -0.2 -0.6 0 20 40 60 time [s] -0.4

0.8 0.6 0.4 0.2 0.0 -0.2 -0.4

(dm/dt)/i (dm/dt)/i (x10

46

Current density (mA/cm2)

mass change current density

1.2
current density i [mA/cm

current density i [mA/cm

1.0

-3

-3 ) (x ) 10 [ng/cm

Potentiodynamic polarisation curves on Fe25Cr in 0.1M H2SO4 + 0.4M Na2SO4

Potentiodynamic measurement of the mass and current density for an Fe25Cr alloy in sulfuric acid. (Polarisation rate: 20mV/s).
4

(dm/dt)/i as a function of the potential for Fe25Cr (a) et detail of the active region (b).
current density |i| [mA/cm
4 2

Current density (mA/cm2)

0
2)2

Mass change (ng/cm mass change m [ng/cm

-3 10 -3 ) (dm/dt)/i (x ) [ng/cm

-2000 -4000 -6000

mass change current density

-0.1 1
6

-0.2 -0.3

4 2

8 6 4

0.1
6 4

(dm/dt)/i (x10

-0.4 (dm/dt)/i current density -0.5 0.0 0.5 1.0 1.5 Potential E (vs. SHE) [V]

0.01

-8000
8 6

0.1

b
s mA] 0.0 -0.1
-3 10 -3 ) (dm/dt)/i (x ) [ng/cm 2

4 2

-0.5

0.0

0.5

1.0

1.5

Potential E (vs. SHE) [V]

1
6

-0.2 -0.3

4 2

Mass decrease in the passive film Dissolution during film formation

0.1
6 4

(dm/dt)/i (x10

-0.4 (dm/dt)/i current density -0.5 -0.40 -0.30 -0.20

Current density (mA/cm2)

2

-10000

Current density (mA/cm2)

2

s mA]

0.0

current density |i| [mA/cm

]
-0.10 Potential E (vs. SHE) [V]

0.01

current density |i| [mA/cm ]

47

Potentiodynamic polarisation curves on pure Cr in 0.1M H2SO4 + 0.4M Na2SO4

Potentiodynamic measurement of the mass and current density for pure Cr in sulfuric acid. (Polarisation rate: 20mV/s).
mass change m [ng/cm Mass change (ng/cm2) -1.56 -1.58 -1.60 -1.62 -1.64x10
4

10

Current density (mA/cm2)

mass change current density

100

Ratio (dm/dt)/i as a function of the potential for pure Cr (polarisation rate: 20mV/s).
s mA]

current density |i| [mA/cm

-3 ) (dm/dt)/i (x-310 ) [ng/cm

0.0 10 -0.1 -0.2 -0.3 0.1 -0.4 -0.5 -0.5 0.0 0.5 1.0 1.5 Potential E (vs. SHE) [V] 0.01 (dm/dt)/i current density 1

0.1

0.01 -0.5 0.0 0.5 1.0 1.5 Potential E (vs. SHE) [V]

(dm/dt)/i (x10

Mass increase in the passive domain Stable oxide

48

Current density (mA/cm2)

2

0.1

100

current density |i| [mA/cm

Transpassive dissolution

49

Potentiodynamic polarisation curves on pure Fe17Cr33Mo in 0.1M H2SO4 + 0.4M Na2SO4

Potentiodynamic measurement of the mass and current density for an Fe17Cr33Mo alloy in sulphuric acid. (Polarisation rate: 20mV/s).
Mass change (ng/cm mass change m [ng/cm
2) 2

0 -2000 -4000 -6000 -8000

10 1 0.1 0.01 0.001 0.0 0.5 Potential vs. SHE [V] 1.0 1.5

Current density (mA/cm2)

100

Ratio (dm/dt)/i as a function of the potential for Fe17Cr33Mo (polarisation rate: 20mV/s).
s mA] 10 -0.1 1 -0.2

current density |i| [mA/cm

mass change current density

0.1

(dm/dt)/i (x10

-10000

-0.3 (dm/dt)/i current density -0.4 0.0 0.5 Potential vs. SHE [V] 1.0 1.5

0.01

Molybdenum suppresses the active dissolution But does not stabilize the passive films (important mass decrease)

50

Current density (mA/cm2)

0.0

current density |i| [mA/cm

-3 10 -3 ) (dm/dt)/i (x )

[ng/cm

Conclusions: dynamic aspects of passive film growth

In acidic and neutral solutions: Films formed on iron-chromium alloys are experiencing a constant dissolution of iron during solution exposure in the passive domain Pure chromium environments oxide is much more stable in these

Molybdenum which is added to obtain high corrosion resistance, does not stabilize the passive film. Higher mass losses are found due to the higher mass of dissolved Mo ions
51