Basic Concepts of Corrosion

Science and Engineering

Corrosion Engineering
ChE 197
We will discuss today the following
topics
Why study corrosion? An intro
Basic concepts of corrosion science and engineering
- What is corrosion; physical processes of degradation;
environmentally assisted degradation processes
- Electrochemical reactions: half-cell, anodic, cathodic,
coupled, atmospheric corrosion, secondary effects of
cathodic reactions
- Simple properties of solutions
- Faraday, Faradays law
- Units for corrosion rates
- Uniform vs localized corrosion
- 8 forms of corrosion
 What is corrosion?
Destructive attack of a metal by its reaction with the environment

There are many specific environments; most general case is a bulk aqueous solution
Atmospheric corrosion aq. solution is a condensed thin-layer solution (not bulk)
We will focus first on metal corrosion; plastics, concrete, wood, ceramics, and
composite materials all undergo deterioration in some environment

Rusting corrosion of iron and plain carbon steel

hydrated ferric oxide; red or dark brown

Steel rusts and corrodes; Al, Cu, Zn (non-ferrous)

corrode but do not rust

White rusting of galvanized steel due to Zn coat

Metals may undergo physical
processes of degradation
Fracture failure of a metal under an applied stress
Fatigue failure of a metal under an applied repeated
cyclic stress
Wear rubbing or sliding of materials on each other
Erosion or cavitation erosion mechanical damage
caused by the movement of a liquid or the collapse of
vapor bubbles against a metal surface
Radiation damage interaction of elementary
particles (e.g., neutrons or metal ions) w/ a solid metal
so as to distort the metal lattice
Physical degradation processes can be assisted/aggravated in the
presence of an aqueous environment

Physical degradation processes and their environmentally assisted counterparts

 Corrosion is an electrochemical process

Usually occurs not by direct chemical reaction of metal with environment

Through the operation of coupled electrochemical half-cell reactions

Half-cell reaction - electrons appear on one side or another of the reaction

Oxidation reaction - electrons are products (right-hand side of the reaction)

Reduction reaction - electrons are reactants (left-hand side of the reaction)
 What are anodic reactions?
Loss of metal occurs as an anodic reaction

Why these chemical reactions anodic?

1. A given species undergoes oxidation
2. There is loss of electrons at the anodic site (electrons are produced by the reaction)
 Are anodic reactions also corrosion
reactions?
Why is this an anodic reaction?

1. Oxidation number of Fe on the left is +2; on the right is +3 increase in oxidation

number for Fe
2. Electrons are produced in the electrochemical half-cell reaction

Also anodic reaction

These are anodic reactions, BUT NOT CORROSION REACTIONS

There is charge transfer, but no loss of metal
Not all anodic reactions are corrosion reactions

Corrosion is the simultaneous transfer of mass and charge across a

metal/solution interface
 What are cathodic reactions?
1. A given species undergoes reduction, i.e., there is a decrease in its oxidation number
2. There is a gain of electrons at the cathodic site (electrons are consumed by the
reaction)
reduction of two hydrogen ions at a surface to form one
molecule of hydrogen gas
predominant cathodic reaction in acidic solutions

reduction of dissolved oxygen to

hydroxyl ions
occurs in neutral or basic solutions
 What are coupled electrochemical
reactions?
On a corroding metal surface, anodic and cathodic reactions occur in a coupled
manner at different places on the metal surface

Coupled electrochemical reactions occurring at different sites on the same metal

surface for iron in an acid solution
Electrons lost by the oxidation of Fe atoms are consumed in the reduction of two H+
ions to form hydrogen gas (H2)
 Why two different electrochemical half-cell
reactions can occur on the same metal surface?
Reason lies in the heterogeneous nature of a metal surface

Polycrystalline metal surfaces contain an array of site energies due to the existence
of various crystal faces (i.e., grains) and grain boundaries

Other defects such as edges, steps, kink sites, screw dislocations, and point
defects; surface contaminants due to the presence of impurity metal atoms or to the
adsorption of ions from solution so as to change the surface energy of the underlying
metal atoms around the adsorbate
Why two different electrochemical half-cell
reactions can occur on the same metal surface?
Metal atoms at the highest energy sites are most
likely to pass into solution
E.g. atoms located at the edges and corners of
crystal planes; stressed surfaces (when metal is
cold worked or shaped)
Once the process of metal dissolution process
begins, a new energy distribution of sites is
established
Positions of anodic and cathodic surface sites
change randomly with time; overall effect is
uniform corrosion of the metal
 What are the four conditions for corrosion
to occur?
You have local anodes and local
cathodes

4 conditions for corrosion to occur

1. An anodic reaction
2. A cathodic reaction
3. A metallic path of contact between
anodic and cathodic sites
4. The presence of an electrolyte

Electrolyte - solution which contains dissolved ions capable of conducting a current

Most common electrolyte is an aqueous solution, i.e., water containing dissolved

ions
Other liquids like liquid ammonia can function as electrolyte
 What are coupled electrochemical reactions in a
neutral or basic aqueous solution?

Coupled electrochemical reactions occurring at different sites on the same metal

surface for iron in a neutral or a basic solution
How does coupled electrochemical reaction in a
neutral or basic aqueous solution continue?

Precipitation of ferrous hydroxide on the iron surface

Conversion of ferrous hydroxide to a hydrated ferric oxide

 What about atmospheric corrosion?
Corrosion of metals in the natural outdoor atmosphere
Do we need an electrolyte for atmospheric corrosion to occur?

Corrosion of iron in air containing 0.01% SO2

after 55 days of exposure showing the effect of
a critical relative humidity (approximately 60%)

Critical relative humidity exists below

which atmospheric corrosion is negligible and
above which corrosion occurs
 What about atmospheric corrosion?
Critical relative humidity is the condition where multimolecular layers of water
vapor physically adsorb from the atmosphere onto the oxide-covered metal surface

Adsorption isotherms for water vapor

on -Fe2O3 showing that multimolecular
layers of adsorbed water are formed at a
relative humidity of 60% and higher

Thin layer of electrolyte required

for atmospheric corrosion is provided at
or above the critical relative humidity
 What are secondary effects of cathodic
reactions?
They do not involve the loss of the metal substrate and thus are not per se corrosion
reactions but

1. Cathodic reaction is coupled to the anodic reaction so that impeding the cathodic
reaction will also impede the anodic reaction
2. Accelerating the cathodic reaction will also accelerate the anodic reaction

3. Cathodic reactions may induce corrosion through secondary effects caused by the
products of the cathodic reaction (examples?)
 What are some examples of secondary
effects of cathodic reactions?

In stress-corrosion cracking, the narrow confines of the stress-corrosion crack limit

the exchange of dissolved metal ions with the bulk electrolyte
Metal cations like Fe2+ ions accumulate within the stress-corrosion crack and are
then hydrolyzed to form hydrogen ions
 What are some examples of secondary
effects of cathodic reactions?

Local environment within the crack tip becomes acidified due to the production of
hydrogen ions; major cathodic reaction is the reduction of hydrogen ions

Hydrogen ions produced within the crack can be reduced to form hydrogen atoms
which adsorb on the metal surface; migrate into the stressed region ahead of the crack
tip; this promotes hydrogen embrittlement (a type of corrosion)
 What are some examples of secondary
effects of cathodic reactions?
In neutral or basic solutions, the major cathodic reaction is the reduction of
dissolved oxygen

In thin-layer electrolyte, like in atmospheric corrosion, continued production of OH

and their accumulation will cause an increase in the pH of the thin layer of solution

If the pH increases, i.e., solution becomes

more alkaline, then corrosion behavior of the
underlying substrate can be altered

Example: Aluminum has low

corrosion rate at pH 7, but the corrosion rate
increases dramatically with increasing pH
 What are simple properties of
solutions?
pH is a measure of the acidity (or alkalinity) of a solution

Lower and higher values are possible (e.g. pH of 12 M HCl is -1.1)

Concentration of hydrogen ions and of hydroxyl ions (OH) in aqueous solutions are
related via the ionization constant for water

When an ionic solid (acid, base, or salt) dissociates into ions in solution:

We define a solubility product:

If the ion product exceeds the tabulated value of Ksp, then precipitation of solid AxBy
occurs
 Example 1
The corrosion of aluminum produces Al3+ ions in solution. Write an expression for the
solubility product of aluminum hydroxide. If the concentration of Al3+ ions in solution is
1.0 106 M, will aluminum hydroxide precipitate at pH 9.0? The tabulated value for
Ksp for aluminum hydroxide is 1.3 1033.

Solution:
Equilibrium between Al(OH)3 and its ions:
Solubility product:
Definition of pH:

Ionization constant of water:

This is greater than the

tabulated Ksp; aluminum
hydroxide will precipitate
 What is Faraday and Faradays Law?
Corrosion is the simultaneous transfer of mass and charge across a metal/solution
interface
Unit of charge is the coulomb; product of the current and its time of passage
Unit of mass is the gram; obtained from the number of equivalents of metal lost
and the equivalent weight of the metal

Faraday is the link between charge transfer and mass transfer

Faradays law describes the mass (W) of metal corroded in terms

of current I (Amperes), time t (seconds), atomic weight of metal A, &
number of equivalents transferred per mole of metal n

n = 2:
n = 3:
 Example 2
Plain carbon steel immersed in seawater has a uniform corrosion rate expressed as a
penetration rate of 5.0 mpy (mils per year, where 1 mil=0.001 in.). The density of iron
is 7.87 g/cm3. The atomic weight of Fe is 55.8 g/mol.
(a) Calculate the weight loss after 1 year.
(b) Calculate the corresponding corrosion current density in microamperes per square
centimeter assuming that the corrosion current is given by

Solution:
Weight loss is given by:

Corrosion current density is :

 What are units for corrosion rates?
Corrosion current density - microamperes per square centimeter, milliamperes per
square centimeter, and amperes per square meter

Mass loss - grams per square centimeter per day and mdd (milligrams per square
decimeter per day)

Penetration rate - ipy (inches per year), inches per month, and mpy (mils per year,
where 1 mil = 0.001 in.); millimeters per year and micrometers per year

Relative severity of
corrosion rates by National
Assoc. Corr. Engg. (NACE)
International
 What is the difference between
uniform and localized corrosion?

In uniform corrosion, metal is attacked more or less evenly over its entire surface
No portions of metal surface are attacked more preferentially than others; metal
piece is thinned away by corrosion until the piece eventually fails

Examples are zinc in hydrochloric acid;

atmospheric corrosion of iron or steel in
aggressive outdoor environments

Positions of localized anodes and

cathodes change with time and dance
all over the metal surface
What is the difference between
uniform and localized corrosion?
In localized corrosion, local anodes
and cathodes exist, but their
positions become fixed so that
corrosion proceeds on established
portions of the metal surface

3 most prevalent forms:

1. Pitting - metal is attacked at certain fixed
sites on the metal surface where the
otherwise protective oxide film breaks down
locally

2. Crevice corrosion - metal within narrow

clearances undergoes localized attack

3. Stress-corrosion cracking - combined action

of an applied stress and a chemical
environment causes the initiation and
propagation of cracks in the metal
 What is the difference between
uniform and localized corrosion?

Example of localized corrosion showing a

hole in automobile muffler caused by
combined action of hot exhaust gases,
condensed moisture, and road spray
consisting of water and de-icing salts

Pitting, crevice corrosion, and SCC share the common feature that there is a
geometrical constraint on the system
1. Pitting - cap of corrosion products above the propagating pit
2. Crevice corrosion - narrow dimensions of the crevice
3. SCC - narrow dimensions of the crack
What are the eight forms of corrosion?
Uniform attack (or general corrosion)
Crevice corrosion
Pitting
Stress-corrosion cracking (SCC)
Galvanic corrosion (two metal corrosion)
Intergranular corrosion
Selective leaching (dealloying)
Erosion corrosion
 What are the eight forms of corrosion?
Galvanic corrosion occurs when two metals are in mechanical or electrical contact.
In a corrosive environment, one of the metals acts as an anode and undergoes
corrosion, while the second metal acts as a cathode and remains unattacked

Intergranular corrosion is the pronounced localized attack that occurs in narrow

regions at or immediately adjacent to grain boundaries of an alloy
- e.g. Type 304 SS (carbon + 18% Cr + 8% Ni) heated at 425 790 0C then cooled

Selective leaching or dealloying is the preferential removal of one element from a

solid alloy by corrosion
- e.g. preferential removal of zinc from copper zinc alloys (dezincification); preferential
removal of iron from gray cast iron (graphitic corrosion)

Erosioncorrosion is caused by the mechanical action provided by the movement of

a corrosive liquid against the metal surface