Corrosion protection

Jacek Bana

University of Science and Technology (AGH-UST) Faculty of Foundry Engineering Department of Chemistry and Corrosion of Metals

Corrosion protection

Corrosion resistant alloys

Coatings
Anodic and cathodic protection Inhibitors

CORROSION PREVENTION Corrosion Resistant Alloys

Metals thermodynamically stable in aqueous environments - noble metals: Cu, Ag, Au, Pt, Pd etc.

Pourbaix diagrams allow to predict stability conditions for pure metals in aqueous solutions (pH, redox potential and concentration of soluble species).
Metals and alloys thermodynamically unstable Corrosion resistance is connected with the passivation of metal surface stainless steels, nickel and nickel alloys, high silicon cast iron, valve metals (Ti, Ta, Al), aluminium alloys. Corrosion resistance is connected with the formation of insoluble layer of corrosion product low alloyed steels (weathering steels), lead, zinc and zinc coatings, tin and tin plates, copper and copper alloys.

CORROSION RESISTANT ALLOYS active, passive and transpassive state

Anodic polarization curves of metal undergoing corrosion and passivation

Alloying by addition of the inhibiting components and components improving protective behavior of surface layer
Some non metallic (P,N, Si) and metallic (Cr, Mo) components of the alloy can accumulate on active places of metal surface during corrosion process. These elements react with the solvent and form non soluble strongly adsorbed compounds on the kinks, steps and structural defects.

The blocking of active areas of the alloy surface leads to the decrease of corrosion rate.

The adsorbed intermediate product can influence kinetics of growth of the layer of corrosion product and can change their microstructure and morphology. The reason of the better

corrosion resistance of weathering steels in atmosphere in compare to ordinary carbon steels

is the presence of small amounts of Cr, Mo, Si, P. The above mentioned elements change the microstructure of iron oxides on the steel surface.

The protective properties of the films formed on weathering steels are connected with the
presence of superparamagnetic goethite and maghemite in the inner layer. The decrease of particle size of goethite and maghemite increases protective behavior of the surface layer. The presence of silicon and phosphorus in the weathering steels stimulates the formation of

superparamagnetic goethite and thus improves the corrosion resistance of the alloys.

CORROSION RESISTANT ALLOYS

Schematic presentation of the factors improving corrosion resistance of active alloys

Optimal composition of carbon steel resistant to hydrogen embrittlement

Component
C Solid state components Si Mn Ni Co Al Carbides formers Cr Mo Ti Nb V

Optimal content %
0.2 do 0.3 0.4 do 0.7 1.2 0.5 do 1.0 0.5 0.25 1.0 do 1.5 0.4 do 0.5 0.05 0.02 do 0.06 0.1

Modifiers REM (Ce) AlN, VN, NbN

Impurities S P Sb Sn Cu

0.1 do 0.3 0.2

0.01 0.015 0.01 0.01 0.05

Passive metals

Passivity promoters and dissolution moderators according to the synergy between the energy of the metal-metal bonds and heat of adsorption of oxygen. P. Marcus: Corr.Sci. 36, 2155 (1994)

Coatings
Coatings of metallic, inorganic and organic materials can provide a satisfactory barrier between metal and its environment and can protect the metal surface against corrosion. The following kinds of anticorrosion coatings can be distinguished: metallic coatings inorganic coatings organic coatings composit materials Metallic coatings: -cathodic (Ni, Cr, Cu and copper alloys, noble metals - Au, Ag, Pt)
These coatings are composed from corrosion resistant metals and in corrosive medium, are more noble than underlying metal surface (are cathodic in reference to the protected metal). The damage of the layer creates the corrosion macro galvanic cell with the anodic underlying metal surface and cathodic metal coating.

anodic (Zn, Cd, Al)

Composed from metals which show more negative stationary potential in corrosive medium (are anodic in reference to the underlying metal surface). These coatings can prevent underlying metal surface even by the damage or perforation of the layer - cathodic protection.

Coatings

Inorganic coatings: oxid films - anodization conversion layers chromates phosphates silica layers ( sol-gel method) enamels Organic coatings: anticorrosion painting polymer coatings

METALLIC COATINGS

Methods of preparation: electrodeposition cementation chemical reduction metallizing - flame spraying cladding Hot dipping vapour deposition diffusion surface modification (laser surface alloying, ion implantation) Electrodeposition Zn+2 + 2e Zn

alcaline or acid media cementation

Fe + Cu+2 Fe+2 + Cu
Chemical reduction Ni+2 + H2P02- + H20 Ni + 2H+ + H2P03-

INORGANIC COATINGS
Oxide films anodization of aluminium: Al + 2H20 AlOOH + 3H+ + 3e oxidation of iron (NaOH + NaN03 + NaN02 (140 - 145C) ): Fe Na2Fe02 Na2Fe204 Fe2O3 * mH20 Conversion layers

nMe+n + mA-n MemAn + mne

chromate layers, phosphate layers

Me 2H 3PO 4 Me(H 2 PO 4 ) 2 2H 2e

Me(H 2 PO 4 ) 2 MeHPO 4 H 3PO 4

3Me(H 2 PO 4 ) 2 Me3 (PO 4 ) 2 4H 3PO 4
3Me 3PO 4 Me 3 (PO 4 ) 2 H 3PO 4

Cathodic protection

Current i

pipe cathode

anode

Cathodic protection

Structures that are commonly protected by cathodic protection are the exterior surfaces of: pipelines ships hulls storage tank bases jetties and harbour structures steel sheet, tubular and foundation pilings offshore platforms, floating and sub sea structures
Cathodic protection is also used to protect the internal surfaces of: large diameter pipelines ships tanks (product and ballast) storage tanks (oil and water) water-circulating systems.

Cathodic protection can be achieved in two ways: - by the use of galvanic (sacrificial) anodes, or - by impressed current.

Anodic protection

Anodic protection

Inhibitors

Adsorption of organic inhibitor onto a metal surface in aqueous environment

Inhibitors
Physical Adsorption - is the result of electrostatic attrative forces between inhibiting organic ions or dipoles and the electrically charged surface of metal. The surface charge can be defined by the potential of the metal (Ecorr) vs. its zero-charge potential (ZCP, Eq=0). When the difference = Ecorr - Eq=0 is negative, cation adsorption is favored. Adsorption of anion is favored when is positive. Chemisorption - involves charge sharing or charge transfer from the inhibiting molecule to the metal surface in order to form a coordinating type of bond. Inhibition efficiency of homologous series of organic substances differing only in the heteroatom: P>Se>S>N>0

Inhibitors

(a) anodic inhibitors: phosphates silicate compounds

(b) Cathodic inhibitors (c) mixed anodic and cathodic inhibitors poly-phosphates amines Ca(HCO3)2 selenides methylamino-phosphate

Inhibitors
Types of Corrosion Inhibitors
Organic
These materials are characterized by high molecular weight structures, incorporating nitrogen or phosphorous groups. They are usually highly polar molecules. Phosphate Esters Phosphonates

Inorganic
Salts of some metals and amphoteric elements act as corrosion inhibitors. Quite often these materials have tenacious filmforming or passivation effects. In some instances, they react with the metal surface. Chromate Salts Zinc Salts Molybdate Compounds Phosphates Nitrite Salts Silicate Compounds

Control Questions

1. Write down Butler-Volmer equation for reaction: Fe + Cl- =FeCl++e 2. Define corrosion potential of metal. 3. Define polarisation resistance. Discuss its importance for corrosion rate monitoring. 4. Write down the mechanism of iron passivation in aqueous solutions. 5. Is passivation of metals possible in nonaqueous solutions? Explain its mechanism. 6. What is the reason of better corrosion resistance of weathering steels and low-alloyed steels in aqueous solutions? 7. Give the main principle of stainless steel chemical composition selection. 8. Describe the principles of charting Pourbaix diagrams. 9. Write down reactions of atmospheric corrosion of iron under country atmosphere (lack of air pollution). 10 Write down the mechanism of carbon steel corrosion in H2O-CO2 solutions. 11. Discuss the main reason of hydrogen corrosion of metals. 12. What is the noxious effect of sulphate reducing bacteria (SRB) on corrosion resistance of metals? 13. Discuss principles of cathodic corrosion protection. 14. Discuss principles of anodic corrosion protection. 15. What is the protective effect of zinc coatings 16. What are the conversion coatings? Give examples.