Corrosion protection: short overview and summary

Corrosion protection: possible strategies

1) Intrinsic active protection 1a) Modification of the material
Materials Aggressive medium

1b) Modification of the medium

Materials Aggressive medium

2) Extrinsic protection: Separation with the medium

Materials Aggressive medium
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Active corrosion protection: surface passivation !!!

Addition of Cr and Ni changes completely the passivation behavior of steel and allows to obtain a good corrosion protection. Passivation is a good active corrosion protection method. Active protection in this context refers to a protection present from the alloy side and available at any time.

Active corrosion protection of steel II

Alloying elements are the best way of performing active corrosion protection.
Current density
icrit

They have an influence on: - Critical current density icrit (Cr,Mo) - Passive current (Cr)

Ecorr

Potential

Alloys

Icrit [A/cm2]

- Stability domain (Mo)

Active corrosion protection of steel III

- Nickel is essentially playing a role and obtaining the FCC austenitic structure which is much less sensitive to hydrogen embrittlement (hydrogen diffusion is hindered). - The BCC structure of Fe-Cr ferritic stainless is as corrosion resistant as the austenitic one for the other type of corrosion mechanisms. It is only extremely susceptible to SCC. - Nitrogen is also an element allowing to maintain the austenitic structure and can allow to reduce the Ni content of an alloy. Nickel is very expensive, so it is an important factor. - Nitrogen containing steel are prone to the formation of unstable nitrides when exposed to higher temperatures. These ones act as localized corrosion attack sites and decrease the corrosion resistance drastically (alloys difficult to weld)

Limit of the active corrosion protection with alloying elements: Aluminum alloy
Example of 2024T3: Large intermetallics (useless) Micrometer domain Dispersoids (strengthening) nanometer domain

SEM/ EDS:
Particles 1 - 4: Al-Cu-(Fe, Mn) Particles A - C: Al-Cu-Mg

TEM/EDS
Al2Cu
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Active corrosion protection: modification of the media

Goal: modification of the environment in order to decrease the corrosion reaction rates. This strategy is used when nothing can be done to increase the intrinsic corrosion resistance of the material:

1) Cathodic protection 2) Anodic protection 3) Inhibitors

Corrosion protection with external applied currents

i

V
Cathodic protection Corrosion Anodic protection Only passive metals

Protection with electrical current/ voltage generators: Rebars, Pipelines, water tubes, aso Protection with sacrificial anodes: Zinc, Magnesium, Aluminum Anodic protection only in chemical reactors for example. The risk of localized corrosion is too high if the environment is not very well know

Cathodic protection with sacrificial anodes

Galvanic coupling can be used to protect structure - For example: Mg, Zn anodes contacted to Steel

Sacrificial anode Steel tank

- Be careful to the electrolyte (soil) conductivity - Do not use cathodic protection on materials unstable in the alkaline domain (For example Al alloys)

Cathodic protection with current / potential generators

A controlled well defined current is applied between the structure (pipe, tank) to protect and an inert electrode located in the ground near to the structure
Power generator Surface

- Used when the efficiency of the sacrificial anodes are not guaranteed

Soil Pipe Pipe or or tank tank

Cable

Inert electrode

- Main disadvantage of the method: it is extremely expensive for large structure

C, Pt, Pb

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Cheap version: cathodic protection of coated surface

Two processes are extremely expensive: - Provide large amount of current for cathodic protection - A perfect, defect-free coating

95% coverage for a coating is easily realizable The current necessary is reduced by 20

Costs for the corrosion protection

Minimal costs for corrosion protection Costs for the coating

Costs for the cathodic protection

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% unprotected metal

Use of corrosion inhibitors

Definition: a species that reduces the corrosion rate of a material when added to an aggressive electrolyte. They are classified in three categories:

1) Adsorption inhibitors:
Substances that reduces the reaction rates through physical or chemical adsorption on the surface

1) Passivating substances:
Substances that favors passivation by influencing the anodic partial reaction

1) Passivators:
Substances that influence passivation by modification of the cathodic reaction
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Adsorption inhibitors
Used mainly against uniform corrosion in acidic media In any case Icorr is reduced

A)

B)
A) Anodic inhibitor Corrosion potential increase Ex: Dimethylchinoline B) Cathodic inhibitor Corrosion potential decrease Ex: Aethylamine C) Mixed inhibitor Corrosion potential stays constant Ex: amines

C)

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Passivating agents
Mechanism: decrease the anodic reaction to lower values than the cathodic reaction rate Example:

Species increasing the pH, OH

Risk: Avoid for materials unstable in the alkaline domain
Current density

E
Ecorr,2 Ecorr, 1 Ecorr, 3

O2 reduction, passivator 14

Passivators
Mechanism: increase the cathodic reaction to a point that stable passivation is reached
Acceleration due to insufficient inhibitor amount

Example:

Cr2O72-, NO2-

Risk: If the concentration is insufficient, corrosion acceleration occurs instead of inhibition

Current density

Potential

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Metallic coating: Sacrificial coatings

Corrosion behavior of noble coatings
Corrosion

Corrosion behavior of active coating

Corrosion

Nickel

Zinc

Fe

Fe

- Nickel coatings have to be extremely protective (without defects) to act as corrosion protection for iron - Zinc coating will just corrode instead of Iron
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Metallic coating: use and problems

- Due to the galvanic coupling occurring between the coating and the underlaying substrate, use of metallic coating is limited to specific field of application. - Noble coatings like Ni only if the coating quality can be very good or in absence of chloride. - Noble coating containing Au, Ag, Pt, if the esthetic aspect of the surface is the dominant factors (jewelry, watches). A very important aspect related to electrochemical cathodic metal deposition is that it is very often accompanied by cathodic hydrogen reduction. Substrate susceptible to hydrogen induced stress corrosion cracking are not indicated for these processes. - Sacrificial Zinc anodic coating is the most important application of metallic coatings !
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Metallic coating: surface processing

Pretreatment Degreasing, etching (possibly sandblasting) clean, roughening, better adhesion Etching through molten metallic salt Wetting, roughening, even better adhesion Dipping process Base metal and molten coating material react together Formation of an alloyed intermediate layer Coating thickness depends on immersion time, bath temperature and composition, dimension and base materials composition Remove excess coating Protect with chromate or phosphate conversion coating
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Post-treatment

Possible coating: Zinc, Aluminum, Tin, lead

Metallic coating: Hot (dip) galvanized steel

Significance Coating structure 1 Mio t Zinc to protect 10000 t Steel

Influence of the Si content in the Steel Main danger: Liquid metal Embrittlement

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Inorganic coating: anodic oxide growth on Al alloys

The principal types of galvanostatic (applied current density) anodizing processes: 1) chromic acid 2) sulfuric acid Produces a thick porous film (for practical use, between 5 -20 m, hardcore process 50 m ) The surface need to be sealed (close the pores) to eliminate the path between the underlying metal and the environment. Usually slight acidified hot water is used Such coating are serviceable in a pH range between 4 to 8.5.
From the surface Pore In a cross section

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Anodizing: the pretreatment question

Al 5XXX serie alloys : rolled sheets, thickness: 1.2mm
Alloy 2-B57s 1-Base 3-Hi Cu 5-Hi Fe 6-Lo Si Full name Alloy 2 (commercial) Alloy 1 (Base) Alloy 3 (Hi Cu) Alloy 5 (Hi Fe) Alloy 6 (Lo Si) Raffinal Aluminium Si* 0.11 0.26 0.26 0.30 0.03 0.0017 Fe* 0.24 0.13 0.11 0.63 0.12 0.0004 Cu* 0.020 0.001 0.170 0.001 0.001 0.0012 Mn* 0.021 0.001 0.002 0.005 0.001 < 0.0001 Mg* 0.85 0.50 0.49 0.54 0.46 0.0002 Zn* 0.004 0.005 0.005 0.005 0.005 < 0.0005 Fe:Si 2.1 0.5 0.4 2.1 3.9

Alkaline Etching Solutions: comparable to commercial etchant Amount 100 g/l 10 g/l 20 g/l Molarity 2.5 M 0.05 M 0.77 M Ingredient NaOH Sodium gluconate Alloy 2 (commercial) Major impurities Fe: < 5 ppm Cu: < 0.2 ppm Fe: < 0.001% Pb: < 0.002%
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Etching is very sensitive to small alloy composition changes

SEM and AFM images of polished and etched surfaces.
polished etched 10 s @ 60 C etched 60 s @ 60 C etched 60 s @ 60 C

Alloy 2 (commercial)

Alloy 3 (Hi Cu)

Alloy 5 (Hi Fe)

5 m

5 m

20 m

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Surface protection: thin dense vs. thick porous on Mg alloys

Thin, dense
Potential (V)

pH13, 0.05M Na3PO4

Current density (mA/cm
200 16 14

FIB: Ion-beam image

Thickness: 1.2-1.8 nm/V

150

12 10

Platinum layer for FIB sectioning Mg hydroxide / Phosphate Mg alloy

100

8 6

50

i=
0 0 100 200

15mA/cm2
300 400

2
2

) 500

Time (s)

3M NaOH / 0.6M KF / 1.1M NaAlO2 / 0.21M Na3PO4

100

Sample 2
80

80 10

Potential [V]

60 60 40

-3

Current [A]

Thick, porous

40

20

20

i= 80 mA/cm2
0 0 100 200 300 400

Potential Current
0 500 600

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Time [s]

Anodizing: additional information's

Corrosion resistant surface 1) Additional layer: porous anodized oxides serves as bases for good adhesion of polymer top coats 2) Color pigments or inhibitors can be integrated in the pores 3) Disadvantage of thick porous oxides is that they are brittle and crack very easily. Corrosion protection is locally suppressed
Anodizing is possible on any metals and alloys that can produce an insulating oxide: Al, Ti, Mg, Ta, Zr (not exhaustive list) For semiconducting oxides (example: steel), the applied anodic current is used to dissociate water ! No anodizing possible
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FIB section

Active Agents released from the pores

Conversion coating: principle

The term conversion coating comes from the fact that film growth is the result of reduction of an high valence ion present in solution Typical : Chromate, Phosphate, Titanate, Zirconate At the same time, metallic atoms from the surface are oxidized to form a mixed oxide. For example Al-Cr mixed oxide for Al alloys.

The result is a rapid and technically simple process + Other advantages compared to other processes Is it a perfect corrosion protection method ? no, chromate is carcinogenic and needs to be replaced sooner or later
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Reactions taking place during a conversion coating process

Cr2O7-2 fast Cr(III)
Cr2O7-2 slow Cr(III) Al+3

Fe(CN)6-4 fast Fe(CN)6-3

Al0

Al+3

Al0

Cr2O7-2, HCrO4Cr(III)/Cr(VI)
2Cr O 2 7 Cr (III) hydroxide

mixed oxide

L. Xia, R. L. McCreery,, J. Electrochem Soc. 1999, 146, 3696-3701

AA 2024-T3

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Reduction of Cr(VI) and role of intermediate species

1400

Raman 860 cm-1 peak height (AU)

AA2024-T3:

1200 1000 800 600 400 200 0

Fe(CN)63IrCl62V3+ Fe3+

Cr2O72-

Fe(CN)64-

Al3+

Cr(III)

Fe(CN)63-

Al

No mediator
0 50 100 150 200 250 300 350

immersion time (seconds)

AA2024-T3 very slowly reduces Cr2O72AA2024-T3 rapidly reduces Fe(CN)63Fe(CN)64- rapidly reduces Cr2O72IrCl62- can substitute as mediator
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L. Xia, R. L. McCreery,, J. Electrochem Soc. 1999, 146, 3696-3701

Self healing properties of chromate conversion coating

The coating (or primer) provides a stable

reservoir of Cr6+
chromate from primer coat

Cr6+ remains stable (for some significant time)

solution

Cr6+ is leached by contact with solution Cr6+ hydrolyzes to an anionic species that migrates to defects

HCrO4-/CrO42-/Cr2O72-

labile Cr6+

conversion coating mixed Cr(III)/Cr(VI) oxide deposit

At the defect, chromate is reduced and precipitated as a mixed Cr(III)/Cr(VI) oxide where it inhibits cathodic rxns, or At the defect chromate absorbs into aluminum hydroxide gel stabilizing it and preventing further corrosion.
Zhao, JES, 145, 2258 (1998).
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Al alloy substrate

Reduction of Cr(VI) and role of intermediate species

originally coated alloy surface inhibitor reservoir incipient protective layer due to action of inhibitor originally bare alloy surface defect

The cell permits examination for: Release of active agent into solution (UV absorption or ICP-OES) Deposition of the active agent on the defect (Auger microscopy or Electron Microprobe) Corrosion resistance of the simulated defect Corrosion resistance of the original coating. (Electrochemical Impedance spectroscopy EIS)
Zhao, McCreery, Frankel, JES, 145, 2258 (1998). 29

10 to 5000 m 0.5 to 0.05M NaCl

Cerium as inhibitor for possible chromate replacement

Anodic oxidation Al Al3+ + 3 eAl oxide

Cathodic reduction O2 + 2H2O + 4e4OHIMP

Al matrix

Pourbaix-Diagram of Ce
[M. Pourbaix, Atlas of Electrochemical Equilibria Aqueous Solutions (Houston, Tx: NACE, 1974), p.183]

Solubility-Diagram of Ce
[Buchheit RG, M.S., Schmutz P, Guan H, Active corrosion protection in Ce-modified hydrotalcite conversion coatings. CORROSION, 2002. 58(1): p. 3-14.]

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Cerium blocks the local cathodic activity

6016 Alloy, 350 C, 15h, fresh polished
Electron microprobe (EPMA) mapping of a surface immersed in 1M NaCl + 10mM CeCl3 for 12 min not immersed to CeCl3 12min immersed to 10mM CeCl3 + 1M NaCl

30m

31

Electrochemical Impedance spectroscopy

Ohms law gives a simple relation E=I*R When AC signal are involved the relation is Eac = Iac * Z Z: impedance

Simple model
-for electrochemical Interface

Rp Rs

Amplitude

I
Rs : Rp : C:

C
solution resistance polarization resistance of the surface capacitance of the surface
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- Apply voltage perturbation (10 mV) - Measure the current response in function of frequency

EIS results on self-healing properties of a coating

10 6
Ce-modified HT
2 2) ) (ohmcm Rp R (ohm*cm c

10 5 10 4 10 3

Cerrate conversion control

6 8 Time (hrs)

10

12

Bare 2024-T3 is exposed to Ce coatings and control samples in the

artificial scratch cell for 48 h Surfaces are removed and placed in contact with aerated 0.05 M NaCl EIS spectra are collected vs. exposure time and Rp is computed
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Hydrotalcite structure can accommodate various species in their structure

LiAl(OH)3+ ZnAl(OH)32+ CeO2 MnO4VO3V10O286MoO42Fe(CN)64-/3NO3-

50 mm

1 m

10

Ce objectives: incorporate Ce oxyanion in the HT interlayer. have HT release oxyanions upon contact with solution. exploit Ce redox chemistry to induce self-healing.

[Buchheit RG, M.S., Schmutz P, Guan H, Active corrosion protection in Ce-modified hydrotalcite conversion coatings. CORROSION, 2002. 58(1): p. 3-14.]

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Smart combined coating to replace chromate

Non-chromate Inhibitor Identification and Delivery-on-Demand
Solubility and signal for demand is controlled via

multiple mechanisms (1) Incorporation into the galleries of hydrotalcite crystals powders (2) Packaging of inhibitor solids via plasma polymerization

Inh.

(3) Containment within sol gel nano-capsules having pores with controlled release gates.

A- A-

Amorphous, Field-Applied Metalic Cladding

TEM BF micrographs of Al90Co3Ce7 alloy in the as-cast and heat treated conditions.

Polymer coating
As-cast 270C

AA 2024-T3

Composed of Al-TM-RE with a composition that retains amorphicity at slow cooling rates Upon aging, amorphous structure transforms to nano-crystallite particulates within amorphous matrix - amorphous character retained Provides initial and most important line of corrosion protection 35 Also improves fatigue resistance

Filiform corrosion under organic coatings: optical observation

When an organic coating is mechanically damaged, undermining of the coating occurs. Corrosion filaments propagate at the interface polymer/ metal (or oxide)

Coated Aluminum

Coated Steel

Filiform Corrosion On scratched Al surface

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Filiform corrosion: damages

Polymer Coating SEM of cross section Al-Alloy with intermetallic particles

Corroded area Corrosion Products back of head: oxygen reduction (at the intermetallic particles ?) active head (AlCl3 solution): Al dissolution

Plane-view photograph

Electrochemical Mechanism: Al is dissolved in the active head, the anode. The electrons set free by this reaction are used at the cathode, behind the active head, to reduce oxygen.
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Filiform corrosion mechanisms

Filiform corrosion (FFC) is a special case of an aeration cell. Requirement for initiation:
- High relative humidity - Water and air can diffuse through the organic layer - there must be a defect in a coating (scratch, pinhole) - Salt must be present in the defect
Anode (Acidic) Al alloy with intermetallic particles Membrane Corrosion products Polymer coating

Cathode (Alkaline)

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Corrosion protection methods: summary

Metallic coatings provide good mechanical properties to the surface.
Disadvantage: conducting therefore risk of accelerating the substrate corrosion because of galvanic coupling (except sacrificial coatings)

Inorganic coating provide good corrosion resistance.

Disadvantage: anodized or thermal oxides are brittle and do not withstand applied stress. Anodizing might also be an expensive process

Conversion coating: adherent surface layer of low solubility oxide, phosphate or chromate.
Disadvantage: the more efficient species are toxic

Organic coatings: Inert barrier layer, usually epoxy resins, polyurethane top coat (essentially paint the surface)
Disadvantage: soft compared to the other type of coating. Can be easily damaged and then corrosion can proceed
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