Corrosion PHD ShortCourse2

Corrosion - fundamentals
David Trejo and O. Burkan Isgor
OSU Doctoral Short Course (Trejo/Isgor) July 10-14, 2017 Slide 1

Introduction

Corrosion
• Generic definition:
The destruction or deterioration of a material because of reaction with its

environment. (Fontana)
• Specific definition (for our purpose):
The destructive result of electrochemical reaction between an elemental

metal or metal alloy and its environment. (Jones)

Corrosion Cycle
Ore
Metal Alloys,
Oxides Metals
Alloys in
Corrosion
Service
Think of it as nature’s way of minimizing total energy… It is also said to be

“extractive metallurgy in reverse…”

Rusting vs. Corrosion
• “Rusting” is a term dedicated to the changes in physical
appearance of iron and ferrous alloys (e.g. steels, cast
irons, etc.) during corrosion.
• All non-ferrous metals corrode, but do not rust (e.g. copper,

aluminum, etc.)

Chemical vs. Electrochemical
• Chemical reaction: process in which one or more substances, the
reactants, are converted to one or more different substances, the
products.
• Reactions occur due to changes in bond structure.
• Examples:
– 𝐴𝐴 + 𝐵𝐵 → 𝐴𝐴𝐴𝐴 (synthesis)
– AB ---> A + B (decomposition)
– A𝐵𝐵 + 𝐶𝐶 → 𝐴𝐴 + 𝐵𝐵𝐵𝐵 (single displacement)
– AB + CD ---> AD + CB (double displacement)
– HA + BOH ---> H2O + BA (acid-base)
– CxHy + (x + y/2)O2 ---> (x) CO2 + (y/2) H2O (combustion)

Chemical vs. Electrochemical
• Electrochemical reaction: process either caused or
accompanied by the passage of an electric current and
involving in most cases the transfer of electrons between
two substances—one a solid and the other a liquid.
• Example: Redox reactions
– Ox: Oxidation reaction
• Where electrons are produced Fe→ Fe2+ + 2e-
• Anode
• Metal loss (corrosion)
– Red: Reduction reaction
• Where electrons are accepted / consumed
• Cathode ½ O2 + H2O + 2e- → OH-
• No metal loss

A Note: Elemental Metal vs. Alloy
Iron-
Carbon
Phase
Diagram

• An alloy is a material with metallic properties that is composed
of two or more substances, of which at least one must be a
metal.
• Steel is an alloy composed of iron and carbon (up to 1.7%),
along with additional alloying elements.
– The amount of carbon and the level of impurities and additional
alloying elements determine the properties of each steel grade.
– There are over 3500 grades of steel.

• Steel differs from cast iron, which is also an iron-carbon alloy.
• Cast iron also contains high Si content (1-3%)
• Cast iron has higher carbon content (greater than 1.7%)
• Steel is malleable; cast iron is mostly not.
• Steel is mostly ductile; cast iron is brittle.

Types of Steel
• Carbon steel
– Only iron and carbon as main components
• Alloy steel
– Manganese is greater than 1.65%, silicon over 0.5%,
copper above 0.6%, or other minimum quantities of alloying
elements such as chromium, nickel, molybdenum, or
tungsten are present
• Stainless steel
– Grades of steel that contain more than 10% chromium, with
or without other alloying elements.

Definitions

Corrosion Definitions
In electrochemical corrosion, four things are for corrosion to occur:
Anode: site where metal is lost and

electrons are produced
Electrolyte
Cathode: site where the electrons
produced at the anode are consumed Ionic path
Metal: path that conducts electrons
from the anodes to the cathodes
Electrolyte: path for the ions, and Anode Cathode
source of reactants
Current path
If you have all four, you have a corrosion cell. Metal

ANODE:
- The electrode of an electrochemical cell at which
oxidation occurs
- Electrons are produced
Salt water
- Electrons flow in the metal away from the anode,
while positive-ion current leaves the anode to return Ionic path
to the electrolyte. Fe2+
- Metal ions enter solution at the anode, and hence,
corrosion of metals usually occurs at the anode. Anode Cathode
- Metal loss, pitting, corrosion is observed at the 2e-
anodes.
Current path Fe
Fe→ Fe2+ + 2e-

CATHODE:
- The electrode of an electrochemical cell at which
reduction is the principal reaction.
- Electrons flow in the metal toward the cathode, and
positive-ion current flows to the cathode from the Salt water
electrolyte. Ionic path
- Typical cathodic processes are cations taking up electrons
OH-
and being discharged, oxygen being reduced, and the O2
reduction of an element or group of elements from a Anode Cathode
higher to a lower valence state.
2e-
Current path Fe
½ O2 + H2O + 2e- → OH-

Corrosion - Definitions
• Oxidation: M → Mn+ + n(e-+)
– e.g. Fe→ Fe2+ + 2e-
– e.g. Al→ Al3+ + 3e-
• Reduction:
– Most commonly electron are consumed in reactions of gasses:
• e.g. ½ O2 + H2O + 2e- → OH- (oxygen reaction)
• e.g. 2H+ + 2e- → H2 (hydrogen evolution)
– Can also be on metal surface (galvanic corrosion):
• Ca+2 +2e-→ Ca

• Electrode: where a half-cell reaction takes place.
– anode or cathode
• Electrolyte: where ions move and react. It is mostly a liquid, but can also
be a solid, that conducts electricity by the flow of ions: the more ions you
have the higher the conductivity.
– E.g. seawater – highly conductive (pure water is not a good
electrolyte because it is not conductive).
– e.g. pore solution in concrete

Ions are charged species: H+, Cl-, SO4-2, OH- ,…
• Anions have negative charges and ‘move’ through the electrolyte to the
anode
• Cations have positive charges and ‘move’ through the electrolyte to the
cathode
• Ions exist in the electrolyte…

There are 4 main types of corrosion cells:
• Dissimilar Electrode Cell

– e.g. Galvanic cell
– e.g. Dry cell
• Concentration Cell
– e.g. Salt concentration cell
– e.g. Differential aeration cell
• Differential Temperature Cell
• Local-action cells

Dissimilar Electrode Cells
(Galvanic cell)

Dissimilar Electrode Cells: dry cell
Source: Uhlig and Revie

21
Concentration Cell
Salt concentration cell:
• Copper plates out on the

electrode (cathode) in the
concentrated solution.
• The electrode (anode) on the

left dissolves.
• This tends to make the

concentrations equal, at which
point corrosion stops.
Source: Uhlig

Concentration Cell
Differential aeration cell:
The region with less oxygen

corrodes (anode).
Oxygen is reduced at the

cathode in an effort to make the
oxygen concentrations equal.
Source: http://www.misumi-techcentral.com

Differential Temperature Cell
Electrodes of the same metal;
but at different temperatures
(e.g. heat exchangers, boilers,
immersion heaters).
Generally, hot metal is the

anode – release overexcited
(hot) electrons. But there are
exceptions depending on the
metal. Sometimes, electrons
can reduce cations on the hot
side of the electrolyte –
Source: Corrosion Doctors
making it the cathode.
24
Local Action Cells

Local Action Cells
Example: Zinc corrosion in de-aerated HCl
Hydrogen evolution may also be observed in steel corrosion in concrete if there is no oxygen
available in the pore solution…

How do we study corrosion?

Standard Hydrogen Electrode (SHE)
1 mol /lt = 1M
http://alevelchem.com

Standard Half-cell Electrode
Potentials

Standard Half-cell Electrode
Potentials
EMF Series

Half-cell Potentials

• We can measure half-cell potentials using reference
electrodes:
– SHE (Standard Hydrogen Electrode)
• H2 → 2H+ + 2e- (Eo = 0.0 V at 25oC)
– CSE (Copper-Copper(II)sulfate Electrode)
• Cu → Cu2+ + 2e- (Eo = 0.337 V vs. SHE at 25oC)
– SCE (Standard Calomel Eelctrode)
• 2Hg→ Hg22+ + 2e- (Eo = 0.788 V vs. SHE at 25oC)

Reference Electrode
Source: Fisher Scientific

SCE (Standard Calomel Electrode):
2Hg→ Hg22+ + 2e- (Eo = 0.788 V vs. SHE at 25oC)

Identify the anodic and

cathodic reactions for the
pairs below:
– Au + Ni
– Pt + Ag
– Au + Pt
– Cr + H2O + O2
– Fe + H2O + O2
– Fe + H2

Galvanic Corrosion
• When two dissimilar metals are connected in an electrochemical
cell (e.g. touch each other in a conductive medium)
– Two different metals
– Electrically connected
– In the same electrolyte
• More anodic metal corrodes
• Less anodic metal is protected
• Galvanic series predicts the corroding metal

Galvanic Series

Forms of Corrosion
• Uniform (general) corrosion
• Pitting corrosion
• Crevice corrosion
• Galvanic corrosion
• Environmentally induced corrosion cracking
– Stress corrosion cracking
– Corrosion fatigue cracking
– Hydrogen induced cracking
• Inter-granular corrosion
• De-alloying corrosion
• Erosion corrosion and fretting

Forms of Corrosion
(Source: Principles and Prevention

of Corrosion by Jones)
Corrosion Rate in Practice:
Mils penetration per year (MPY) = (534 W) / (DAT) (www.nace.org)
W = weight loss in milligrams Metric conversion:

D = density in g/cm3 1 mpy = 0.0254 mm/yr
A = area in square inches
T = time in hours mm/yr = (87.6 W) / (DAT)
(1 mil = 0.001 in) All units the same except for A in cm2

Forms of Corrosion

Forms of Corrosion

of Corrosion by Jones) (http://www.metallurgist.com)
(Uhlig and Revie)
(www.nace.org)

Forms of Corrosion

of Corrosion by Jones) (www.nace.org)
Dissimilar electrode corrosion

Forms of Corrosion

of Corrosion by Jones)
If the crevice is formed by a non-metallic

(www.nace.org)
material, it is sometimes called “deposit
corrosion” or “gasket corrosion”.
A form of concentration cell corrosion.

Thermodynamics of corrosion

Potential-pH (Pourbaix) Diagrams
Example: Aluminum

Potential-pH (Pourbaix) Diagrams
E-pH diagram for pure Al at 25˚C in

aqueous solution.
Sukiman et al. 2012

Potential Anodic Reactions for Iron

Pourbaix Diagram for Iron
Simplified E-pH diagram for pure Fe at 25˚C in

aqueous solution.

Example Pourbaix Diagrams
GREEN: Passive regions; RED: Corrosion regions; GREY: immunity regions
NOTE: Pure gold does not corrode in aqueous environments assuming water is pure
and no other half-cell reaction occurs at a potential higher than 1.5 V (SHE).
(Source: U. of Cambridge - DoITPoMS)

Regions in the Pourbaix Diagram
• Immunity: Corrosion does not occur; i.e., metal ion
activity in the solution does not exceed 10-6 M.
• You keep a metal in this region to protect it from

corrosion by using an external power source. This is
called “cathodic protection”.

• Corrosion: Both metal and its oxides/hydroxides are
unstable; therefore, they corrode; their ionic
concentrations exceed 10-6 M in the solution.

• Passivation: Oxides/hydroxides are stable and in
equilibrium with the soluble solution species. Generally
if the metal is covered with an oxide/hydoxide layer.
• If this layer is called a passive layer if
– it is protective
– has low solubility (less than 10-6 M)

Limitations of Pourbaix Diagrams
• They provide no information on kinetics (how fast the
corrosion will take place).
• They are obtained for specific temperatures and
pressures.
• They are obtained for pure water as the base electrolyte.
• The oxides shown in the diagram as thermodynamically
stable are not necessarily protective (passivating).

Passive Layers
• A passive oxide film needs to have the following
properties:
– Low dissolution rate
– Continuity over the metal surface
– Good mechanical stability

Pilling-Bedworth (P-B) Ratio

Pilling-Bedworth (P-B) Ratio
(Source: NACE)

Kinetics of corrosion

Kinetics
• So far we studied the equilibrium conditions to
understand if corrosion is thermodynamically possible
or not.
• We never discussed how fast the reactions can take
place; i.e., kinetics of corrosion.

Remember - Equilibrium
Time

Kinetics
• To study kinetics we need a different setup for
experiments: three-electrode corrosion cell
(aseptec.com)

Kinetics

Anodic Polarization

Anodic Polarization
Corrosion 62
Example: Mild steel in 10% sulfuric acid

Cathodic Polarization

Activation Polarization:
Tafel Behavior

Activation Polarization:
Tafel Behavior

Mixed Potential Theory

Corrosion current density
Corrosion potential

Passive Metal
icorr = ipass

Zinc in H2SO4 Lead immersed in H2SO4

Iron exposed to natural Magnesium exposed to
waters natural waters
Iron immersed in a
chromate solution
Porous insulating covering

a metal surface

Polarization Types
• Activation polarization
– Both at the anode and cathode
• Concentration polarization
– Mostly at cathode
• Resistance polarization (iR drop)
– Due to the electrolyte
Polarization = over-potential = over-voltage

Activation Polarization – Tafel Behavior

Activation
Polarization

Corrosion current density
Corrosion potential
Anode: Activation Polarization; Cathode: Activation Polarization
74
Modeling of corrosion
(of steel in concrete)

Estimating Corrosion Rates (models)
• Empirical models: Alonso, Duracrete, Liu and Weyers, Ahmad and Bhattachajee,
Morinaga, Trejo et al., etc.
• Analytical models: Bazant, Balabanic et al., Raupach, Gulikers, Huet et al.,
Maruya, etc.
• Numerical models: Krank and Sagues, Isgor, Pour-Ghaz et al., Song et al., etc.
TYPICAL INPUT DATA (varies by model)

• General concrete properties (e.g. w/c, moisture content)
• Chloride content
• Electrical resistivity of concrete
• Half-cell potentials (and/or their gradients)
• Seasonal environmental data (temperature, RH, etc.)
• Oxygen content at steel level

Estimating Corrosion Rates (Exp.)
Weyers and Liu: Chloride content (Ct), temperature(T), resistivity (Rcon)
3006
ln1.08i corr =7.89 + 0.7771ln1.69C t − − 0.000116R con + 2.24t 0.215
T
Trejo et al.: Chloride content (Cl) and threshold (ClTh), w/c, temperature (T), moisture content (mc)
Pour-Ghaz, Isgor, and Ghods: Half-cell potentials (f), cover thickness (d), temperature (T), resistivity (r)

Corrosion Modelling (Numerical)
• The potential mapping of a reinforced concrete
member can be modelled by solving Laplace’s
equation with the following boundary conditions:
∇ 2φ = 0
ia
Anodic sites: φ=
a φFe + β a log
i a
i
Cathodic sites: φ
=c φO + β c log c
i 2
oc
1 ∂φ
Corrosion rate on the surface of the steel: =i = f (φ , r )
r ∂n

Domain and Boundary Conditions
∂φ
=0
∂n
∂φ
=0
∂n
∂φ
=0
∂n
Active area Passive area
Anode Cathode
φa φc
∇ φ =0
2

Typical Results - Potentials

Typical Results – Current Densities
On the steel surface

Typical Results

Typical Results

Typical Results

David Trejo
David.Trejo@oregonstate.edu
O. Burkan Isgor
Burkan.Isgor@oregonstate.edu

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Corrosion - fundamentals

David Trejo and O. Burkan Isgor

OSU Doctoral Short Course (Trejo/Isgor) July 10-14, 2017 Slide 1

OSU Doctoral Short Course (Trejo/Isgor) July 10-14, 2017 Slide 2

The destruction or deterioration of a material because of reaction with its

• Specific definition (for our purpose):

The destructive result of electrochemical reaction between an elemental

OSU Doctoral Short Course (Trejo/Isgor) July 10-14, 2017 Slide 3

Think of it as nature’s way of minimizing total energy… It is also said to be

OSU Doctoral Short Course (Trejo/Isgor) July 10-14, 2017 Slide 4

• All non-ferrous metals corrode, but do not rust (e.g. copper,

OSU Doctoral Short Course (Trejo/Isgor) July 10-14, 2017 Slide 5

• Reactions occur due to changes in bond structure.

OSU Doctoral Short Course (Trejo/Isgor) July 10-14, 2017 Slide 6

OSU Doctoral Short Course (Trejo/Isgor) July 10-14, 2017 Slide 7

OSU Doctoral Short Course (Trejo/Isgor) July 10-14, 2017 Slide 8

OSU Doctoral Short Course (Trejo/Isgor) July 10-14, 2017 Slide 9

OSU Doctoral Short Course (Trejo/Isgor) July 10-14, 2017 Slide 10

OSU Doctoral Short Course (Trejo/Isgor) July 10-14, 2017 Slide 11

OSU Doctoral Short Course (Trejo/Isgor) July 10-14, 2017 Slide 12

Anode: site where metal is lost and

OSU Doctoral Short Course (Trejo/Isgor) July 10-14, 2017 Slide 13

Fe→ Fe2+ + 2e-

OSU Doctoral Short Course (Trejo/Isgor) July 10-14, 2017 Slide 14

½ O2 + H2O + 2e- → OH-

OSU Doctoral Short Course (Trejo/Isgor) July 10-14, 2017 Slide 15

OSU Doctoral Short Course (Trejo/Isgor) July 10-14, 2017 Slide 16

OSU Doctoral Short Course (Trejo/Isgor) July 10-14, 2017 Slide 17

• Ions exist in the electrolyte…

OSU Doctoral Short Course (Trejo/Isgor) July 10-14, 2017 Slide 18

• Dissimilar Electrode Cell

OSU Doctoral Short Course (Trejo/Isgor) July 10-14, 2017 Slide 19

OSU Doctoral Short Course (Trejo/Isgor) July 10-14, 2017 Slide 20

Source: Uhlig and Revie

• Copper plates out on the

• The electrode (anode) on the

• This tends to make the

OSU Doctoral Short Course (Trejo/Isgor) July 10-14, 2017 Slide 22

The region with less oxygen

Oxygen is reduced at the

OSU Doctoral Short Course (Trejo/Isgor) July 10-14, 2017 Slide 23

Generally, hot metal is the

OSU Doctoral Short Course (Trejo/Isgor) July 10-14, 2017 Slide 25

Example: Zinc corrosion in de-aerated HCl

OSU Doctoral Short Course (Trejo/Isgor) July 10-14, 2017 Slide 26

OSU Doctoral Short Course (Trejo/Isgor) July 10-14, 2017 Slide 27

OSU Doctoral Short Course (Trejo/Isgor) July 10-14, 2017 Slide 28

OSU Doctoral Short Course (Trejo/Isgor) July 10-14, 2017 Slide 29

OSU Doctoral Short Course (Trejo/Isgor) July 10-14, 2017 Slide 30

OSU Doctoral Short Course (Trejo/Isgor) July 10-14, 2017 Slide 31

OSU Doctoral Short Course (Trejo/Isgor) July 10-14, 2017 Slide 32

Source: Fisher Scientific

OSU Doctoral Short Course (Trejo/Isgor) July 10-14, 2017 Slide 33

Identify the anodic and

OSU Doctoral Short Course (Trejo/Isgor) July 10-14, 2017 Slide 34

OSU Doctoral Short Course (Trejo/Isgor) July 10-14, 2017 Slide 35

OSU Doctoral Short Course (Trejo/Isgor) July 10-14, 2017 Slide 36