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What is Corrosion?

IMC207: CIENCIA DE LOS


MATERIALES I

Corrosion is the oxidation of a metal due to an


ELECTROCHEMICAL reaction. The oxidizing agent is
most often O2 (atmospheric corrosion) or H+ (chemical
corrosion) or both.

Corrosin y degradacin

Henry A. Colorado, PhD

Why is it a problem?

Mechanical Engineering Department


Universidad de Antioquia
From, Materials science and engineering an introduction, William D. Callister (Wiley)

Chapter 17 - a

Financial - $350 Billion Dollar Annual Problem in U.S.


(4.25% of GNP) Department of Defense spends $6
8 Billion
Chapter 17 -

Corrosion Mechanism

Basics of Corrosion

Cathodic cell
discussion of emf
galvanic series
intergranular corrosion
oxidation-reduction of iron
salt effects

EMF series is a numeric rating of potential


under ideal conditions
Galvanic Series is a practical listing
Galvanic Protection

Chapter 17 -

Chapter 17 -

Recipe for corrosion

EL COSTO DE LA CORROSION

Active metal

Water
Oxygen
(atmospheric corrosion)
Acid
(chemical corrosion)
Salt
Chapter 17 -

High temperature

Chapter 17 -

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Chemical vs. Atmospheric Corrosion


(H+ vs. O2)

Oxidation - Reduction Reduction


Anodic metal gives up electrons
(oxidation)

Eo red (V)
Anodic Reaction:
Fe0(s)
Fe2+(aq) + 2e- Deterioration of metal
Cu(s)
Cu2+(aq) + 2eAg(s)
Ag+(aq) + eCathodic Reaction:

Fe Fe 2 2e
Al Al 3 3e

Cathodic metal accepts electrons


(reduction)

2H+(aq) + 2e-

2H

4e-

O2 (g) + 4H+(aq) + 4e-

Or gases accept electrons (reduction)

2e H2 ( gas)

4OH-

(aq)

+0.40

Atmospheric

2H2O (l) Combination

+1.23

Which of these will oxidize copper? Silver? Gold?

Eocell (V)

Overall Reaction:
Fe0(s) + 2H+(aq)

Fe2+(aq) + H2 (g) Chemical

2Fe0(s) + O2 (g) + 2H2O (l)


2Fe0(s) + O2 (g) + 4H+(aq)

+0.44

2Fe2+(aq) + 4OH-(aq) Atmospheric

+0.84

2Fe2+(aq) + 2H2O (l) Combination

Chapter 17 -

+1.67
Chapter 17 -

Why wont iron corrode in pure (degassed) water?


Eo

+0.34
0.00

H2 (g) Chemical

O2 (g) + 2H2O (l) +

Cu 2 2e Cu

-0.44
+0.80
+1.50

Steel Corrosion

(V)

Anodic Reaction:
Fe0(s)

Fe2+(aq) + 2e-

-0.44

Initial Oxidation Reaction

Cathodic Reaction:
2H2O (l) + 2e-

H2 (g) + 2OH-(aq)

2 Fe O2 2 H2 O 2 Fe ( OH ) 2

Eocell (V)

Overall reaction:

Fe0(s) + 2H2O (l)

-0.83

Fe2+(aq) + H2 (g) + 2OH-

Secondary Oxidation Reaction

-0.39

(aq)

1
2 Fe(OH ) 2 O2 H2 O 2 Fe(OH ) 3
2

What metals will corrode in pure (degassed) water?


Any sufficiently active metal Eored < -0.83 V

Rust

(alkali metals, alkaline earth metals, aluminum, manganese)


Chapter 17 -

Chapter 17 -

Example of Atmospheric
Corrosion

Example of Chemical Corrosion


Nuclear Reactor Vessel Head
Degradation

Corrosion on wing of Navy aircraft

F/A-18C Hornet

Why does corrosion of an


airplane occur primarily
while the plane is on the
ground?
Chapter 17 -

February 16, 2002, Davis-Besse Nuclear Power Station in Oak Harbor,


Ohio

Boric Acid leak from


control rod drive
mechanism led to
chemical corrosion of
reactor vessel head
Serious potential for loss of
reactor coolant access

Chapter 17 -

How might this corrosion


be minimized?

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Corrosion of a Ships Hull


Anodic and Cathodic Regions
O2

Salt

Hull of
ship

O2 + 2H2O + 4eFe2+ + 2OHFe(OH)2


4Fe(OH)2 + O2
+ 2H2O

Preventing Corrosion

Cathodic
Region
RUST

4OHO
H-

Anodic
Region

e-

2(Fe2O3H2O)

Fe
2+

Fe2+ + 2e-

Fe

Electrons Migrate
from Anodic to
Cathodic Region

High pH (> 9)
Chapter 17 -

Preventing the Corrosion of Iron


(cathodic protection/sacrificial anode)

Chapter 17 -

Applications of Cathodic Protection


Galvanized Steel
Zinc coating

Sacrificial Anodes

Sacrificial anode

Ship Hulls
Subs (free flooding areas)
Los Angeles Class Sub

Arleigh-Burke Destroyer

Chapter 17 -

Impressed Current Cathodic


Protection
Shipboard Power

Galvanic Corrosion
(contact between unlike metals;
opposite of cathodic protection)

Paint
Layer

Shipboard Power

O2
Controller

Power Supply

H2O

Reference
Electrode

Copper

Hull

e-

Chapter 17 -

e-

Cathode:
O2 + 2H2O + 4e- 4OH-

Iron
Anode:
Fe Fe2+ + 2e-

Pt Anode
Insulation
Chapter 17 -

Chapter 17 -

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EL COSTO DE LA CORROSION

COROSION DE ZINC EN ACIDO

Corrosion:

Se requieren dos reacciones:


Zn Zn2 2e
-- oxidacion:

-- the destructive electrochemical attack of a material.


-- Al Capone's

2H 2e H2 (gas)

-- reduccion:

ship, Sapona,
off the coast
of Bimini.

H+
Oxidation reaction
Zn
Zn 2+
H+

Photos courtesy L.M. Maestas, Sandia


National Labs. Used with permission.

Zinc

Cost:

flow of e- 2e in the metal

H+
H+

Acid
solution

H+
H+

H2(gas)
H+
reduction reaction

-- 4 to 5% of the Gross National Product (GNP)*


-- this amounts to just over $400 billion/yr**

Adapted from Fig. 17.1, Callister 7e.


(Fig. 17.1 is from M.G. Fontana,
Corrosion Engineering, 3rd ed.,
McGraw-Hill Book Company, 1986.)

Other reduction reactions:


* H.H. Uhlig and W.R. Revie, Corrosion and Corrosion Control: An Introduction
to Corrosion Science and Engineering, 3rd ed., John Wiley and Sons, Inc.,
1985.
**Economic Report of the President (1998).

-- in an acid solution

O2 4H 4e 2H2O

-- in a neutral or base solution

O2 2H2O 4e 4(OH)

Chapter 17 - 19

Chapter 17 - 20

STANDARD HYDROGEN (EMF) TEST

STANDARD HYDROGEN (EMF) TEST


Two outcomes:

H2(gas)
Mn+ H+
ions
H+

e2e -

25C

e-

ne metal, M

metal, M

ne -

--Metal sample mass

e-

Platinum

e-

Mn+
ions

H+ 2e H+

Platinum

--Metal sample mass

25C

1M Mn+ soln 1M H+ soln

1M Mn+ soln 1M H+ soln

--Metal is the anode (-)

--Metal is the cathode (+)

o
Vmetal
0 (relative to Pt)

o
Vmetal
0 (relative to Pt)
Adapted from Fig. 17.2, Callister 7e.

Standard Electrode Potential


Chapter 17 -

Chapter 17 - 22

STANDARD EMF SERIES

more anodic

more cathodic

EMF series
metal
Au
Cu
Pb
Sn
Ni
Co
Cd
Fe
Cr
Zn
Al
Mg
Na
K

Metal with smaller


o
o
Vmetal
Vmetal
corrodes.
+1.420 V
Ex: Cd-Ni cell
+0.340
+
- 0.126
- 0.136
- 0.250
DV o =
- 0.277
0.153V
- 0.403
Cd
Ni
25C
- 0.440
- 0.744
- 0.763
1.0 M
1.0 M
- 1.662
Cd 2+ solution Ni 2+ solution
- 2.363
- 2.714
Adapted from Fig. 17.2, Callister 7e.
Data based on Table 17.1,
- 2.924 Callister 7e.
Chapter 17 - 23

Chapter 17 -

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Corrosion potential calculation


Reduction Reaction must have higher
potential than the oxidation reaction or
they will not form a cathodic cell

Potentiodynamic Polarization
Curve

Fe 2 2e Fe

-0.440 V

Zn 2 2e Zn

-0.763 V

DV .440 .763 0.323V

Chapter 17 -

Relative measure of
corrosion
Chapter 17 -

GALVANIC SERIES

more anodic
(active)

more cathodic
(inert)

Ranks the reactivity of metals/alloys in seawater


Platinum
Gold
Graphite
Titanium
Silver
316 Stainless Steel
Nickel (passive)
Copper
Nickel (active)
Tin
Lead
316 Stainless Steel
Iron/Steel
Aluminum Alloys
Cadmium
Zinc
Magnesium

Based on Table 17.2, Callister


7e. (Source of Table 17.2 is
M.G. Fontana, Corrosion
Engineering, 3rd ed., McGrawHill Book Company, 1986.)

Chapter 17 - 27

Chapter 17 -

Chapter 17 -

Chapter 17 -

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Acceleration of Corrosion
Physical Characteristics
exposed area (less, increases corrosion rate)
time of exposure (more time, more corrosion)

Environmental Characteristics

acidic environment
sulfur gas environment
temperature (high temps, more corrosion)
moisture (oxygenated moisture)

Chapter 17 -

Passivation

Chapter 17 -

FORMS OF CORROSION
Stress corrosion

A protective film in oxidizing atmospheres


chromium,nickel, titanium, aluminum

Metal oxide layer adheres to parent metal


barrier against further damage
self-healing if scratched

Sensitive to environmental conditions


passivated metal may have high corrosion
rates

Uniform Attack
Oxidation & reduction
occur uniformly over
surface.

Selective Leaching

Intergranular
Corrosion along
grain boundaries,
often where special
phases exist.

attacked
zones

Forms of Corrosion

Fig. 17.18, Callister 7e.

Erosion-corrosion
Break down of passivating
layer by erosion (pipe
elbows).

Pitting

Preferred corrosion of
one element/constituent
(e.g., Zn from brass (Cu-Zn)).

g.b.
prec.

Chapter 17 -

Stress & corrosion


work together
at crack tips.

Forms
of
corrosion

Galvanic
Dissimilar metals are
physically joined. The
more anodic one
corrodes.(see Table
17.2) Zn & Mg
very anodic.

Downward propagation
of small pits & holes.
Fig. 17.17, Callister 7e.
(Fig. 17.17 from M.G.
Fontana, Corrosion
Engineering, 3rd ed.,
McGraw-Hill Book
Company, 1986.)

Crevice Between two


pieces of the same metal.
Rivet holes

Fig. 17.15, Callister 7e. (Fig. 17.15 is


courtesy LaQue Center for Corrosion
Technology, Inc.)
Chapter 17 - 34

Forms of Corrosion

Uniform corrosion of a single metal


usually an electrochemical reaction at
granular level
relatively slow and predictable
rusting of exposed steel, tarnished
silver
easily corrected with coatings and
regular maintenance

Chapter 17 -

Galvanic Corrosion
2 dissimilar metals, electrolyte,
electrical connection and oxygen
Pitting Corrosion
Localized corrosion forming holes or
indentations
Difficult to initially detect

Chapter 17 -

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Forms of Corrosion

Forms of Corrosion

Crevice Corrosion
narrow crevice filled with ionized
solution
Oxygen-rich on the outside, oxygenpoor on the inside
metals oxidize with salt anions FeCl2
and pH rises in cathodic zone
H+ may destroy passivity

Intergranular Corrosion
corrosion along grain boundaries at
microscopic level
stainless steels and heat treated highstrength steels
carbides precipitate along grain
boundaries leaving these areas with no
alloyed Chromium
Welds can have this same depletion
effect

Chapter 17 -

Forms of Corrosion

Chapter 17 -

Forms of Corrosion

Cavitation and Erosion in Pipe


particulate matter
turbulent flow
abrades away the corrosion product
abrasion of zinc coatings

Stress Corrosion Cracking


tensile stress and corrosive
environments
cracks are initiated at corrosion areas
tensile stresses propagate the crack
corrosion further deteriorate crack
etc.....

Chapter 17 -

Reinforcement Corrosion

Chapter 17 -

Corrosion of Metals in Concrete


Reinforcing Steel & Prestressing
Steel
Concrete is Normally Highly Alkaline
Protects Steel from Rusting if Properly
Embedded

If Corrosion Occurs, the Reaction Products


are
Greater in Volume Than the
Original Steel
Corrosion Initiation and Rate Depends On
Amount of Concrete Cover, Quality of Concrete
Details of Construction, & Exposure to Chlorides
Chapter 17 -

Chapter 17 -

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CONTROLLING CORROSION
Metal oxide
Metal (e.g., Al,

Self-protecting metals!

-- Metal ions combine with O


stainless steel)
to form a thin, adhering oxide layer that slows corrosion.

Reduce T (slows kinetics of oxidation and reduction)


Add inhibitors
-- Slow oxidation/reduction reactions by removing reactants
(e.g., remove O2 gas by reacting it w/an inhibitor).
-- Slow oxidation reaction by attaching species to
the surface (e.g., paint it!).

Cathodic (or sacrificial) protection


-- Attach a more anodic material to the one to be protected.
Adapted
from Fig.
17.23,
Callister
7e.
Chapter 17 -

Corrosion Prevention
Coatings

Barrier films
Inhibitive Pigments
Sacrificial treatments
Paint

e.g., zinc-coated nail


Zn 2+

zinc

zinc
2e - 2e steel

e.g., Mg Anode

steel
pipe

e-

Cu wire
Mg Mg 2+
anode
Earth

Adapted from Fig. 17.22(a),


Callister 7e. (Fig. 17.22(a) is
from M.G. Fontana, Corrosion
Engineering, 3rd ed., McGraw-Hill
Book Co., 1986.)
Chapter 17 - 44

Activation polarization

Active Cathodic
Protection

Chapter 17 -

Chapter 17 -

Chapter 17 -

Chapter 17 -

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Chapter 17 -

Chapter 17 -

Chapter 17 -