Fundamentals of Corrosion

Brett Tossey
AEP BRO 2014

DNV GL 2013

SAFER, SMARTER, GREENER

Introduction
Definition of Corrosion
Electrochemistry Fundamentals
Theory (just a bit)
Thermodynamics
Kinetics

Forms of Corrosion

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Corrosion Definition

What Is Corrosion??
Degradation of a material through environmental interaction.

Steel = thermodynamically unstable

Steel is found in nature as an ore (iron oxides)
We put energy into it to convert it to an alloy
It wants to revert back to the oxide
Lowest energy state

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Life Cycle of Steel

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Why Steel (or Iron-Based Alloys)

Readily available
Can be inexpensive
Wide variety of processing techniques
Strong
Ductile

Versatile
Wide range of alloys to achieve desired properties
Strength, ductility, hardenability
But, susceptible to corrosion

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Corrosion
All forms of aqueous corrosion are electrochemical in nature
Metal oxidation:
M

M+ + e-

Reduction reaction to consume electrons

O2 + 2H2O + 4e2H+ + 2e-

4OHH2

Charge transfer between locations of oxidation and reduction reactions

Both reactions required for corrosion to occur

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Corrosion
LEO says GER (Losing Electrons Oxidation, Gaining Electrons Reduction)
Oxidation Reaction (loss of e- ,) = Anodic Reaction
Occurs at Anode
M

M+ + e-

Reduction Reaction (gain of e-) = Cathodic Reaction

Occurs at Cathode
O2 + 2H2O + 4e-

4OH-

Both reactions required for corrosion to occur

A reduction reaction must be present to consume electrons liberated by
oxidation reaction

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Differential Corrosion Cell

Four Components
Anode
Cathode
Electrically conductive metallic path
Between anode and cathode

Electrolyte
Ionically conductive path
Between anode and cathode
e.g., soil

Corrosion morphology related to spacing between anode and cathode

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Differential Corrosion Cell

e-

e-

Anodic Reaction
Metal loss from oxidation reaction
Fe(s)
Fe 2+ (aq) + 2e-

eeionic current flow

(dissolved, charged species)

Direct
current flow
eeee

Cathodic Reaction
Reduction of Oxygen
e-

Alloy Substrate
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O 2 (do) + H2O (aq) + 4e-

4OH-(aq)

How Do We Detect Ongoing Corrosion?

Monitor voltages and currents associated with corrosion
Voltage develops across metal- electrolyte interface when metal is placed in
electrolyte
Referred to as corrosion potential
Cannot measure it directly

Can measure it with respect to a reference electrode (RE)

Copper Sulfate Electrode (CSE) commonly used for soils
Seawater RE = Silver / Silver Chloride
Common laboratory RE = Calomel

Solid RE = Platinum wire

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Test Methods:
Potential Measurements
Does not yield information on corrosion rate
Provide means to measure oxidizing power of the environment
The more positive (noble) the potential, the stronger the oxidizing power of the
medium
Provide ranking of relative nobility of materials
Used to predict galvanic couple activity

Measure Voltage (Potential)

Of Corrosion Cell

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Potential Measurements

Measure Voltage (Potential)

Of Corrosion Cell

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How Do We Detect Ongoing Corrosion?

Potentials related to relative corrosion resistance of a metal in a given
environment
Gold and Platinum very positive
Magnesium and Zinc very negative

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Metal or Alloy

Potential (V,CSE)

Platinum

0.2 to -0.1

Copper

-0.3

Mill Scale on Steel

-0.3

Lead

-0.5

Rusted Mild Steel

-0.2 to -0.5

Clean Mild Steel

-0.5 to -0.8

Aluminium

-0.8

Zinc

-1.1

Magnesium

-1.75

How Do We Detect Ongoing Corrosion?

Current measurements
Measure potential gradients in soil or metal
V = IR (where anode and cathode are separated)
Other electrochemical techniques

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Thermodynamics
Tells us whether a reaction will occur
One principle of Thermodynamics
Material seeks lowest energy state
Gibbs free energy (G)
G < 0 for process to be thermodynamically favored

G related to electromotive force (E)

G = - zFE
z = valence change for reaction
F = Faradays Constant

A positive value of E indicates that a reaction (combination of two half reactions)

is favored

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Thermodynamics
Steel is thermodynamically unstable in water
water reduction can promote corrosion
2H2O + 2e-

2OH- + H2

But rates are low

Hydrogen reduction occurs in acid environments

2H+ + 2e-

H2

Oxygen reduction is most common reduction reaction associates with corrosion

O2 + 2H2O + 4e-

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4OH-

Kinetics
Tells us the rate of a reaction
Electrical current related to corrosion rate through Faradays Law

m/at = iM/zF
m = mass, t = time, a = exposed area

i = current density, M = atomic weight, z = electrons transferred, F =

Faradays constant
Corrosion Rate = (m/at)1/ i = Current Density
= metal density
For steel, 1 mil per year (0.001 in/yr) ~ 2 A/cm2

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Evans Diagram
Plot showing corrosion kinetics
Potential vs log current
Polarization = deviation in potential as a result of passage of current
Reactions are linear on plot for simplest type of behavior
Activation polarization

Limiting reaction is e- transfer

Another common type of polarization
Concentration polarization
Diffusion controls corrosion rate

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Evans Diagram
Ecor (corrosion potential) occurs where sum of oxidation reactions = sum of
reduction reactions
No net accumulation of charge

Net current is zero at Ecor

Slopes of lines = Tafel Slopes

Tafel slopes are not all the same for different reactions
Typically 50 to 200 mV/decade

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Evans Diagram

Potential

2O2 + H2O + 2e- a 4OH-

Ecor
icor
Fe0 a Fe2+ + 2eLog Current Density

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Slide

Evans Diagram
Cant measure corrosion current directly
Cant measure icor
Measure difference between anodic and cathodic reaction
How do we determine icor
Tafel extrapolation

Other calculations
Linear polarization resistance (LPR)

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Kinetics (Polarization)

Polarization Resistance (PR) measurements

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Morphological Forms of Corrosion

Eight common forms of corrosion (Fontana)
General (Uniform) Corrosion
Pitting Corrosion
Crevice Corrosion
Stress Corrosion Cracking

Galvanic Corrosion
Intergranular Corrosion
Selective Leaching (Dealloying)
Erosion Corrosion

Forms in Red affect underground piping

Discussed further

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General (Uniform) Corrosion

Uniform metal loss
Oxidation and reduction reactions are spatially close on the metal surface
Example: steel in hydrochloric acid
Greatest destruction of metal on a tonnage basis
Not usually an economic or integrity concern

Predictable
Can be readily mitigated

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Pitting Corrosion
Localized attack that results in holes or pits in a metal
Cavity with diameter about the same or less than the depth
Can cause failure with only a small percentage weight loss for a metal
Commonly associated with passive alloys
Stainless steels; protective oxide film

Associated with local breakdown

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Pitting Corrosion
Separation of anodic and cathodic reactions on metal surface
Anodic reaction in pit
Reduction reaction outside pit
Autocatylic
Reactions in pit promote continued corrosion

Hydrolysis reactions that reduce pH

Movement of chlorides into pit
Chlorides promote passive film breakdown
Potentials required for hydrogen evolution and ion movement is effected by
electric fields.

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Pitting Corrosion
Carbon steel not considered to be a passive metal
But, pitting in carbon steel does occur
Internal and external pitting associated with microbes
Microbiologically influenced corrosion (MIC)
Internal CO2 corrosion

External stray current corrosion

DC or AC induced
Corrosion attack focused on holidays in coating

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Crevice Corrosion
Localized attack within crevices
Associated with small volumes of electrolyte within the crevices
Environment within the crevice becomes more aggressive with time
Limited oxygen access
pH reduces with time

Similar process to pitting corrosion

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Pit and Crevice pH

Chemistry in pit / crevice vastly different then bulk environment
Crevice pH ~ 1.5 @ [Cr] > 21%; Bulk soln pH = 7.0

pH

Chromium Content in Alloy (wt. %)

29

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Pit and Crevice Chemistry

Chemistry in pit / crevice vastly different then bulk environment

30

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Pit and Crevice Chemistry

Low pH in pit / crevice

River Patterns; Gravity effect

Rapid metal dissolution

Dissolved 22% chrome alloy

3:00

Absorber slurry
pH = 5.5

Horizontal weld seam

Gravity

6:00

31

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Stress Corrosion Cracking (SCC)

Cracking caused by simultaneous presence of
Tensile stress
Susceptible metal
Potent environment
Two forms of SCC

Intergranular
between grains in metal
transgranular cracking
Through grains

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Galvanic Corrosion
Classical Definition - dissimilar metal corrosion
Corrosion as a result of the electrical connection of dissimilar metals in an
electrolyte
More negative member of couple becomes anode
More positive member of couple becomes cathode

Corrosion rate of anode is increased

Polarized in positive direction
Corrosion rate of cathode is decreased

Stainless Steel (~ 22% Chrome)

Polarized in negative direction

Stainless
Steel (18% Cr)
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Galvanic Series in Neutral Soil and Water

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Metal or Alloy

Potential (V,CSE)

Platinum

0 to -0.1

Copper

-0.2

Mill Scale on Steel

-0.2

Lead

-0.5

Rusted Mild Steel

-0.2 to -0.5

Clean Mild Steel

-0.5 to -0.8

Aluminum

-0.8

Zinc

-1.1

Magnesium

-1.75

Stray Current Corrosion

Sources of stray current
Utilities (Pipelines, Overhead Transmission)
Commercial Activities (welding)
Circulating Currents
Unbalanced Transformers (3rd Harmonics)

Long Line Effects

Telluric
Subways, Railroad lines, Mining
Smelting Operations, Welding

Other

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Corrosion Control
Corrosion is inevitable
Goal of corrosion control
Control rate and mode of corrosion to achieve useful life of a structure
Methods of corrosion control
Alloy selection
Compatible with service environment
Component design
Avoid geometries that promote corrosion

Surface preparation
inhibitors
Cathodic protection
Coatings

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