Corrosion Engineering

N Balasubramanian

CHE3166: Materials and Corrosion

Corrosion: ?

Corrosion: Destruction of a material by reaction with its environment. Corrodere (Latin) - To Eat Away

The basic corrosion reaction

M M+ + e Metal becomes a cation Oxidation reaction Electrochemical reaction Need to have a corresponding reduction reaction
4

Cost of Corrosion

Federal Highway Administration (DOT) Office of Infrastructure Research and Development

In Cooperation With: NACE International The Corrosion Society

Cost of Corrosion
Categories Infrastructure Utilities Transportation Production & Manufacturing Government

Cost of Corrosion
Oil & Gas Exploration & Production Mining Motor Vehicles Ships Aircraft Railroad Cars Hazardous Materials Transport TOTAL: 23.4 2.7 2.2 Pulp & Paper 0.5 0.9 29.7 Agricultural Production Food Processing Electronics Home Appliances TOTAL 1.1 1.1 1.5 17.6 6.0 Petroleum Refining Chemical, Petrochemical, & Pharmaceutical 1.4 0.1 3.7 1.7

Cost of Corrosion

forms of corrosion

The eight forms are: 1. uniform, or general attack, 2. galvanic, or two-metal corrosion, 3. crevice corrosion, 4. pitting 5. intergranular corrosion 6. selective leaching, or parting 7. erosion corrosion, and 8. stress corrosion.

Forms of Corrosion

Uniform Corrosion
Galvanic Corrosion Pitting Crevice Corrosion ErosionErosion -corrosion

10

Uniform Corrosion
Uniform attack is the most common form of corrosion. It is normally characterized by a chemical or electrochemical reaction which proceeds uniformly over the entire exposed surface or over a large area. The metal becomes thinner and eventually fails. For example, a piece of steel or zinc immersed in dilute sulfuric acid will normally dissolve at a uniform rate over its entire surface. A sheet iron roof will show essentially the same degree of rusting over its entire outside surface.

11

Forms Of Corrosion
Uniform Corrosion Galvanic Corrosion Pitting Crevice Corrosion Erosion Erosion-corrosion

12

OK?

OK

Dissimilar Metal Couples Graphite Titanium Alloy C-276 Stainless Steel Copper Cast Iron Steel Aluminum Zinc

Can Be Bad

13

Galvanic Corrosion
A potential difference usually exists between two dissimilar metals when they are immersed in a corrosive or conductive solution. If these metals are placed in contact (or otherwise electrically connected), this potential difference produces electron flow between them. Corrosion of the less corrosion-resistant metal is usually increased and attack of the more resistant material is decreased, as compared with the behavior of these metals when they are not in contact. The less resistant metal becomes anodic and the more resistant metal cathodic. Usually thecathode or cathodic metal corrodes very little or not at all in this type of couple. Because of the electric currents and dissimilar metals involved, this form of corrosion is called galvanic, or two-metal, corrosion. It is electrochemical corrosion, but we shall restrict the term galvanic to dissimilar-metal effects for purposes of clarity.
14

Galvanic Corrosion

15

Forms Of Corrosion
Uniform Corrosion Galvanic Corrosion Pitting Crevice Corrosion ErosionErosion -corrosion

16

Pitting Corrosion
Pitting is a form of extremely localized attack that results in holes in the metal. These holes may be small or large in diameter, but in most cases they are relatively small. Pits are sometimes isolated or so close together that they look like a rough surface. Generally a pit may be described as a cavity or hole with the surface diameter about the same as or less than the depth. Pitting is one of the most destructive and insidious forms of corrosion. It causes equipment to fail because of perforation with only a small percent weight loss of the entire structure. It is often difficult to detect pits because of their small size and because the pits are often covered with corrosion products. In addition, it is difficult to measure quantitatively and compare the extent of pitting because of the varying depths and numbers of pits that may occur under identical conditions.

17

Pitting Corrosion

18

Forms of Corrosion
Uniform Corrosion Galvanic Corrosion Pitting Crevice Corrosion ErosionErosion -corrosion

19

Crevice Corrosion
Intense localized corrosion frequently occurs within crevices and other shielded areas on metal surfaces exposed to corrosives. This type of attack is usually associated with small volumes of stagnant solution caused by holes, gasket surfaces, lap joints, surface deposits, and crevices under bolt and rivet heads. As a result, this form of corrosion is called crevice corrosion or, sometimes, deposit or gasket corrosion

20

Crevice Corrosion

21

Forms Of Corrosion
Erosion corrosion is the acceleration or increase in rate of deterioration or attack on a metal because of relative movement between a corrosive fluid and the metal surface. Generally, this movement is quite rapid, and mechanical wear effects or abrasion are involved. Metal is removed from the surface as dissolved ions, or it forms solid corrosion products which are mechanically swept from the metal surface. Sometimes, movement of the environment decreases corrosion, particularly when localized attack occurs under stagnant conditions, but this is not erosion corrosion because deterioration is not increased.

Uniform Corrosion Galvanic Corrosion Pitting Crevice Corrosion ErosionErosion -corrosion

22

Erosion-corrosion

23

Forms of Corrosion
Selective leaching is the removal of one element from a solid alloy by corrosion processes. The most common example is the selective removal of zinc in brass alloys (dezincification). Similar processes occur in other alloy systems in which aluminum; iron, cobalt, chromium, and other elements are removed. Selective leaching is the general term to describe these processes, and its use precludes the creation of terms such as dealuminumification, decobaltification, etc. Parting is a metallurgical term that is sometimes applied, but selective leaching is preferred.

Selective Leaching Intergranular Attack Corrosion Fatigue Environmental Cracking

24

Selective Leaching

25

Forms Of Corrosion
Grain boundary effects are of little or no consequence in most applications or uses of metals. If a metal corrodes, uniform attack results since grain boundaries are usually only slightly more reactive than the matrix. However, under certain conditions, grain interfaces are very reactive and intergranular corrosion results. Localized attack at and adjacent to grain boundaries, with relatively little corrosion of the grains, is intergranular corrosion. The alloy disintegrates (grains fall out) and/or loses its strength.

Selective Leaching Intergranular Attack (IGA) Corrosion Fatigue Environmental Cracking

26

Intergranular Corrosion

Intergranular Corrosion

28

Forms of Corrosion
Stress-corrosion cracking refers to cracking caused by the simultaneous presence of tensile stress and a specific corrosive medium.

Selective Leaching Intergranular Attack Corrosion Fatigue Environmental Cracking

29

Corrosion Fatigue
120 100 80

Stress (ksi)

60 40 20 0 10,000 100,000 1,000,000 10,000,000 100,000,000

Cycles to Failure In Air In Seawater

30

Corrosion Fatigue Fracture

31

Stress Corrosion Cracking

Alloy Susceptible Tensile Stress Specific Corrosive

32

Stress Corrosion Cracking Vertical Heat Exchanger

33

Stress Corrosion Cracking

Stainless Steel/steel Cladding

34

Stress Corrosion Cracking

Caustic Carryover In Steam

35

Forms of Corrosion
Erosion corrosion is the acceleration or increase in rate of deterioration or attack on a metal because of relative movement between a corrosive fluid and the metal surface. Generally, this movement is quite rapid, and mechanical wear effects or abrasion are involved. Metal is removed from the surface as dissolved ions, or it forms solid corrosion products which are mechanically swept from the metal surface. Sometimes, movement of the environment decreases corrosion, particularly when localized attack occurs under stagnant conditions, but this is not erosion corrosion because deterioration is not increased.

Selective Leaching Intergranular Attack Corrosion Fatigue Environmental Cracking

37

Factors Favoring
SCC Stainless Steels
Temperature > 55 C Chlorides Oxygen Evaporative Conditions Pit - Stress Raiser Residual Or Applied Stress

38

Mechanical And Physical Factors

Strength, Ductility Formability Welding, Joining Thermal Conductivity Thermal Expansion Unique Properties

39

Other Factors

Safety Compatibility Availability Cost

40

Economics

Managements Language Is Economics Use Life Cycle Costs To Compare Materials

41

Materials Selection

Define Environment Define Required Equipment Define Test And Inspection

42

Define Environment
Major Reactants Minor Ingredients pH, Contaminants, Aeration Process Conditions Temperature, Pressure, Excursions Catalytic/inhibitive Effects e.g., Metallic Ions

43

Define Equipment
Pressure Vessels Valves And Piping Tankage Utilities Systems

44

Test & Inspection

Fabrication Verify Materials, Workmanship, Dimensions, Storage Conditions Testing & Inspection Develop Program Consider Corrosion Test Locations

45

Dont Expect Inspect

46

CHE3166 Corrosion: Thermodynamics

Net reaction is oxidation of zinc by copper(II) ions: Zn(s) + Cu2+ Zn2+ + Cu(s) Half reactions take place in separate locations: Left electrode: Zn(s) Zn2+ + 2e oxidation Right electrode: Cu2++ 2e Cu(s) reduction

Electrochemical cells allow measurement and control of a redox (reduction/oxidation) reaction. Also, we can force the reaction to proceed in its non-spontaneous, or reverse direction by connecting a source of current to the two electrodes. To sustain the cell reaction, the charge carried by the electrons through the external circuit must be accompanied by a compensating transport of ions between the two cells.
47

Galvanic cells and electrodes

To sustain the cell reaction, the charge carried by the electrons through the external circuit must be accompanied by a compensating transport of ions between the two cells. Relative amounts of charge can be carried by negative or positive ions (depends on their relative mobilities) through the solution. Salt bridge, consists of an intermediate compartment filled with saturated salt solution and fitted with porous barriers at each end, is used for precise measurements. The purpose of salt bridge is to minimize the natural potential difference (junction potential).
48

Thermodynamics
Consider zinc in a solution of hydrochloric acid

Zn + 2 HCl ZnCl2 + H 2
This reaction can be separated into two half-cell reactions

Zn Zn 2 + + 2e 2 H + + 2e H 2

Oxidation reaction (anodic reaction with potential ea) Reduction reaction (cathodic reaction with potential ec)

has an associated free-energy change (G)

G = nFE = nF (ea + ec )

Nernst Equation

n=number of electrons exchanged, F=96500 C/e-, E=potential

49

Standard hydrogen electrode

Pt is inert and acts as catalyst site 1 atm H2 gas is the standard state

Solid Zn and 1N Zn2+ is the standard state Measured potential difference V is 0.762V

50

Standard hydrogen electrode

For a pure Cu electrode in a 1 N Cu 2+ solution, the potential difference in this cell is 1.104 V

Zn 2 + + 2e Zn (0.762V ) Cu 2 + + 2e Cu(+0.342V )

51

Electromotive Force Series

Zn + 2 HCl ZnCl2 + H 2 or Zn Zn 2 + + 2e 2 H + + 2e H 2
E = ea + e c E = +0.762 + 0 E = +0.762V G = nFE < 0
At standard state, reaction will occur
52

Electromotive Force Series

3Pb + 2 Al 3 + 3Pb 2 + + 2 Al or Pb 2 + + 2e Pb Al 3 + + 3e Al E = ea + ec E = +0.126 + (1.662) E = 1.532V G = nFE > 0
At standard state, reaction will not occur
53

Electromotive Force Series

Shipboard corrosion protection

The half-cell reaction with the more active (negative) halfcell potential always proceeds as an oxidation, and the reaction with the more noble half-cell potential always proceeds as a reduction in the spontaneous reaction produced by the pair

54

Electromotive Force Series

Question. Is copper (Cu) oxidized (dissolved) by ferric (Fe3+) ions?

Ferric reduction is noble relative to copper so copper is oxidized (copper becomes an ion and gives off electrons)

55

Reaction Direction

Written as reduction reactions from left to right Hydrogen reduction is chosen (arbitrarily) as the reference and assigned zero potential

56

Standard conditions
Standard states: For a solid, the solid is taken as unit activity For a gas, 1 atm pressure is taken as unit activity For dilute or strongly dissociated solutes typically found in most instances of corrosion, activity is reasonably approximated by the concentration

(A) = CA
A=activity of atom A = activity coefficient (tabulated) CA=concentration (g/l) of atom A
57

Activities

Gases Pure liquids and solids Solutes Liquids in solutions Solvent in dilute solution

A=p (partial pressure in atm) A=1 A=M (molarity) A=X (mole fraction) A=1

58

Non-standard conditions
Analyze a general half-cell equation between atom A and atom B in an aqueous solution

aA + mH + + ne = bB + dH 2O
For reactants and products in the standard state
0 0 0 0 G 0 = (bGB + dG H aG + mG ( A H+ ) 2O )

For reactants and products in a non-standard state

G = (bGB + dG H 2O ) (aGA + mG H + )
59

Non-standard conditions
The departure of free energy in the non-standard state from the standard state is:
0 0 0 0 G G 0 = b(GB GB a G G + m G G + )+ d(G H 2O G H ( ) ( ) A A H H+ ) 2O

][

The corrected concentration A available for the reaction is known as the activity of A and is given by:
0 a(GA GA )= aRT ln( A) = RT ln(A) a

B) (H 2O) ( 0 G G = RT ln a + m (A) (H )

60

Nernst Equation
Recall
G G
0

B) (H 2O) ( = RT ln a + m (A) (H )

G = nFE = nF (ea + ec )
At 25C

RT e = e0 ln nF (A)a (H + )m
a 0

(B) (H 2O)

2.3RT = 0.059 F
+ m

(A) (H ) 2.3RT e=e + log b d nF (B) (H 2O)

0.059 (A) m 0.059 pH e = e0 + log b n B ( ) n
a

Recall

pH = log(H + )
Activity of water=1 for aqueous solutions
61

Electrochemical potential
A) m 0.059 ( 0 e=e + log 0.059 pH b n (B) n
a

Examine specific half-cell reactions

2 H + + 2e = H 2
0 eH + / H = eH 0.059 pH + /H
2 2

Assume 1 atm (H2), so activity=1

As the activity of any dissolved oxidizer (e.g., H+) increases, more noble or positive potentials are routinely measured
62

Electrochemical potential
2 H + + 2e = H 2
0 eH + / H = eH 0.059 pH + /H
2 2

The above reaction occurs in an acid solution. An equivalent reaction in neutral or alkaline solutions is:
2 H 2O + 2e = H 2 + 2OH eH + / H = e0 0.059 pH H+ /H
2 2

The electrochemical evolution of hydrogen is the decomposition of water

63

Potential/pH (Pourbaix) Diagram

oxygen evolution and acidification

For hydrogen evolution at a fixed potential

2 H + + 2e = H 2
0 eH + / H = eH 0.059 pH + /H
2 2

hydrogen evolution and alkalization

as pH increases (H+ concentration decreases), we are less likely to form H2 gas

Note that, consistent with the half-cell potential definitions, the hydrogen line goes through zero potential at zero pH
64

Potential/pH (Pourbaix) Diagram

oxygen evolution and acidification

At higher potential
O2 + 4 H + + 4 e 2H 2O

is feasible
hydrogen evolution and alkalization
0 eO2 / H 2O = eO 0.059 pH 2 / H 2O

Note that, consistent with the half-cell potential definitions, the oxygen line goes through 1.229V at zero pH and 0.401V at pH=14. This reaction is the basis for water electrolysis
65

Potential/pH (Pourbaix) Diagram

Corrosion-soluble ions of the metal are stable Passivation- oxides are stable Immunity-reduced form of the metal is stable

66

Potential/pH (Pourbaix) Diagram

Pourbaix diagram for Al Reaction 1: Metal oxidizes to aqueous cations
M = M n + + ne Al = Al 3 + + 3e
eAl / Al 3+ = e 0 + 0.059 (A) m 0.059 pH log b n B ( ) n 0.059 log(Al 3 + ) 3
a

Independent of pH since no H+ is involved. Only depends on Al3+ activity

67

eAl / Al 3+ = 1.662 +

Potential/pH (Pourbaix) Diagram

Pourbaix diagram for Al Reaction 2: Metal reacts to metal hydroxide or oxide
M + nH 2O = M (OH )n + nH + + ne 2 Al + 3H 2O = Al2O3 + 6 H + + 6e eAl / Al2O3 = 1.55 0.059 pH

At higher pH Al2O3 is formed. At lower pH Al2O3 dissolves to Al3+ Intersection depends depends on Al3+ activity (dashed lines are portions of the reactions with no significance)
68

Potential/pH (Pourbaix) Diagram

Pourbaix diagram for Al The reaction rate constant for
2 Al 3 + + 3H 2O = Al2O3 + 6 H +

is known
H ) ( K= (Al )
+ 6 3+ 2

= 1011.4

For (Al3+)=10-6,
log K = 6log(H + ) 2log(Al 3 + )= 6 pH 2log(Al 3 + ) pH = 3.9

Independent of potential
69

Potential/pH (Pourbaix) Diagram

Pourbaix diagram for Al Reaction 3: Metal reacts to form soluble aqueous anions
n 2m M + mH 2O = MOm + 2 mH + + ne

Al + 2 H 2O = AlO2 + 4 H + + 3e

eAl / AlO
2

eAl / AlO
2

0.059 4 =e + log(AlO2 ) 0.059 pH 3 3 = 1.262 + 0.020log(AlO2 ) 0.079 pH

0 Al / AlO 2

At higher pH, Al2O3 dissolves to AlO270

Pourbaix Diagram Fe
Example 2: stability diagram for iron (little bit complicated). Horizontal lines: reactions are involved with electrons (potential), but independent of pH (H(+a) or OH(-a) ions): Fe2+=Fe3++e Ee=0.771+0.0591lg(aFe3+/aFe2+) Fe=Fe2++2e Ee=0.771+0.0591lg(aFe3+/aFe2+) Vertical lines: reactions are involved with pH, but independent of electrons: Fe3++H2O=FeOH2++H+ lg(aFeOH2+/aFe3+)=-2.22+pH Fe2++2H2O=Fe(OH)2+2H+ lg(aFe2+)=13.37-2pH Diagonal lines: reactions are involved both pH and electrons: Fe2++H2O=FeOH2++H++e Ee=0.877-0.0591pH+0.0591lg(aFe(OH)2+/aFe2+) Fe2++3H2O=Fe(OH)3+3H++e Ee=0.748-0.1773pH-0.0591lgaFe2+ Fe+2H2O=Fe(OH)2+2H++2e Ee=-0.045-0.0591pH 71

Standard Hydrogen Electrode

Platinum Foil suspended in sulfuric acid with unit activity of H+. Platinum is noble and does not participate (acts as catalyst only) Connected to another half-cell through a solution bridge that allows for charge but not mass transfer

72

Ohter Electrodes

73

Questions?

74