Corrosion Engineering

Lecture 3
CHE 311
Corrosion Products
 The corrosion products refer to the chemical substances generated during the
corrosion reactions. They can be soluble, such as zinc chloride (ZnCl 2) or zinc
Sulfate (ZnS), or insoluble such as iron oxides or iron hydroxides. The insoluble
corrosion products are not always visible. For example, the corrosion products
on aluminum and stainless steel are not visible while the corrosion products on
steel are visible.
 The presence of corrosion products is one way to detect corrosion failure. Or
accurate analysis and identification of corrosion products is one of the first steps
in determining the causes of corrosion.  
 Corrosion products (rust or oxides) may form a film (single or multiple) on the
metal surface, which often serves to reduce the corrosion rate. This
phenomenon is called passivity, which is covered later.
Iron
 The corrosion products of iron in aqueous solution and moist air is
called “Rust”. Following table indicates few types of rusts associated
with corrosion of iron.
Name Rust formula Color
Magnetite Fe3O4 Black oxide
Hydrated Fe3O4.H2O(ferrous Green (deep blue in
magnetite ferrite) organic complex)
Ferric oxide Fe2O3 Red brown to black
(Hematite) oxide
Ferrous hydroxide Fe(OH)2 Green to greenish black
oxide
Ferric hydroxide Fe(OH)3 Orange to red brown
oxide
Hydrous ferrous Fe2O3.H2O Red brown
oxide
Ferrous ferrite Fe2O3.FeO Green
Examples of iron rust

 Red–brown flaky rust Black magnetite Blue/green unstable rust

Other iron corrosion products
 When iron is in contact with an environment that contains sulfate
reducing bacteria (SRB), hydrogen sulfide gas (H2S) is observed.
This gas is a corrosive substance and it reacts with iron and form
iron sulfide as a corrosion product:

Fe2 + S2  FeS

 When iron is exposed to acid solution such as HCl, the corrosion

products are FeCl2 (soluble salt) and hydrogen gas:

Fe + 2HCl FeCl2 (s) +H2 (g)

Other Metals
 The corrosion products of non-ferrous metals are called” oxides”.
Examples

Name Oxide formula Color

Zinc zinc oxide (ZnO) White oxide

Copper copper oxide (CuO) Black oxide

Aluminum aluminum oxide (Al2O3)  

Nickel Nickel(II) oxide, NiO Green

Nickel Nickel(III) oxide, Ni2O3 Black

Corrosion Inspection and Monitoring
 Successful industry cannot tolerate major corrosion failures. For this reason,
considerable effort must be expended on corrosion control at the design stage
and also in the operational phase. Corrosion failures will lead to unscheduled
shutdowns, and also may lead to environmental pollution, personal injuries and
fatalities. Typically, once a system (e.g. a plant or equipment) is put into
service, continuous and scheduled maintenance is required in order to keep this
system operating safely, efficiently and economically. Corrosion inspection and
monitoring is one of the basic functions required for safe and efficient industrial
operations.

 Generally Corrosion inspection and monitoring are used to determine the

condition of a system and importantly, to determine how well corrosion control
and maintenance programs are performing.
Example: Cost of Corrosion
The GNP of a certain country is SR 500 billion. Calculate:
 a) The average direct cost of corrosion.
 b) The avoidable cost if useful corrosion control technology is used.
Solution
 The direct cost of corrosion is in the range of 3% to 4% of the GNP. Let
us take the average direct cost of 3.5 % of the GNP.

9 3.5
 a) The average direct cost = ( SR 500 10 )  ( ) = SR 17.5 109
100
 A study mentioned that 15 % of the direct coast could be avoided
when currently available corrosion control technology is used.

15
 The avoidable cost = (SR 17.5 109 )  ( ) = SR 2.629 109
100
Basics in Chemistry
 The acidity and alkalinity of a solution is related to the concentration of
 the positive ions is the H+, and the negative ions is the OH-.If the H+ ions is more
than the OH- ions ,then the solution is said to be acidic. if the OH- ions is more
than the H +ions , the solution is alkaline. The acidity of a solution can be
increased by introducing acids such as HCl or H2SO4,
 Water dissociates to produce equal quantities of H+ and OH -, in this case the
solution is said to be neutral.
 The pH is simply a statement of the H+ concentration in the solution and is
defined by the formula: pH= - log [H+].
 The pH may be measured with a pH meter or calculated. The pH is an index
to indicate the acidity and alkalinity of a solution as such:
 A pH = 7: means the solution is neutral ([H+] = [OH-]).
 A pH > 7: means the solution is alkaline ([H+] < [OH-]).
 A pH < 7: means the solution is acidic ([H+] > [OH-]).

In corrosion, the question often arises “What is the pH of the solution?

Chemical Reaction
 A chemical reaction is a reaction in which only neutral molecules and
positively or negatively charged ions take part, within the exclusion of
electrons.
Examples
 Dissociation of water vapor
2H 2 O ( g )  2H 2 ( g ) + O2 ( g )
 Dissociation of liquid water
H 2 O (l )  H  (aq) + OH  (aq)
 Precipitation of ferrous
Fe 2 (aq) + 2 OH  (aq)  Fe(OH)2 (s )
Electrochemical reaction
 An electrochemical reaction is a reaction that produces or consumes
electrons. When a reactant loses electrons during the reaction, it is called
Oxidation. When a reactant gains electrons during the reaction, it is called
reduction.
 Oxidation and reduction are two types of electrochemical reactions that often
work together. Oxidation and reduction reactions involve an exchange of
electrons between reactants. For many students, the confusion occurs when
attempting to identify which reactant was oxidized and which reactant was
reduced. What is the difference between oxidation and reduction?
 The combination of oxidation and reduction reactions is called redox reaction
(Reduction/Oxidation) and it will produce an overall reaction.
Example: Electrochemical reaction
 Consider the reaction between zinc metal and hydrochloric
acid.
 The oxidation reaction is: Zn(s) → Zn2+(aq) + 2e-
 
 The reduction reaction is: 2 H+ + 2 e- → H2(g)

 The overall reaction: Zn(s) + 2 HCl(aq) → ZnCl2(aq) + H2(g)

 The production and consumption of electrons represent the

flow of current. The driving force for metallic corrosion is a
potential difference between the different materials.
Mechanism of Metallic Corrosion
Current flow (I) Electrical contact (Wire)

(-)
Electron flow (e)
(+)

C
A
A
N
T
O
Ionic current flow H
D
O
E
D
E
Electrolyte

 Electron current flows in the solid conductor (e.g. a wire)

 Ionic current flows in the conducting electrolyte (e.g. Liquid)
 Current (I) flow from the cathode to the anode
 Electron (e) flow from the anode to the cathode
Metallic corrosion
 Metallic corrosion is an electrochemical process consisting of at least two
partial reactions that occur on the metal surface. At anodic areas, metal
dissolution or corrosion occurs. At cathodic areas, reactions such as the
reduction of oxygen or the evolution of hydrogen occur. Electronic charge
moves from the anodic site through the metal to the cathodic site where
electrons take part in the cathodic reactions.
 Example: Iron corroding in water with a near neutral pH, these half cell
reactions can be represented as:
 Oxidation reaction: Fe  s    Fe 2  aq   2e
 Reduction reaction: O2  g   2H 2O  l   4e  4OH   aq 
 Overall reaction: Fe  s  + O2  g   2H 2O  l   Fe(OH) 2 ( s) 
 Rust is then quickly produced by the oxidation of the precipitate.

4Fe  OH  2  s   O2  g   2Fe2O3 • H 2O  s   2H 2O  l 
Hydrous ferrous oxide
Red- brown rust
Reactions in Acids
 Metals corroded or "dissolve" by acids and they yield a soluble salt and
hydrogen gas. Examples:

1. Zn + 2HCl ZnCl2 + H2
Zinc Hydrogen Zinc Hydrogen gas
Metal Chloride Chloride

2. Zn + H2SO4 ZnSO4 + H2
Zinc Sulpharic Zinc Hydrogen
Metal acid Sulphate gas

3. Fe + 2HCl FeCl2 + H2
Iron Hydrogen Ferrous Hydrogen
Metal Chloride Chloride gas

4. 2Al + 6HCl 2AlCl3 +3H2

Aluminum Hydrogen Aluminum Hydrogen
Metal Chloride Chloride gas

 Other acids: phosphoric, hydrofluoric, water-soluble organic acids (e.g.

formic and acetic) also produce soluble salts and hydrogen gas
Dissolved Oxygen
 Acid solutions containing dissolved O2 will be more corrosive than acids
without dissolved O2.
 Environment (electrolyte or solution) contains dissolved O2 is called "aerated
environment"
 Environment free of dissolved O2 is called air –free environment or de-aerated
environment.
Reaction in neutral solutions and alkaline solutions

 The corrosion of metals can also occur in fresh water, seawater, salt solutions
and alkaline or basic media. Water and seawater are nearly neutral.
Examples
Moist atmosphere
 4Fe + or aerated water 4Fe (OH)3 (Ferric Hydroxide)
6H2O + 3O2

 This corrosion reaction is the rusting of iron when exposed to moist

atmosphere or water. During rusting there is an opportunity for drying and
the ferric hydroxide dehydrated and forms the familiar red –brown iron oxide
(rust):
 2Fe (OH)3 Fe2O3 + 3H2O (Ferric Oxide)

 2Zn + 2H2O + O2 2Zn (OH)2 (Zinc hydroxide)

 When drying occurs, we get:
 Zn (OH)2 ZnO + H2O (Zinc oxide)
Basics in Metallurgy
 When a piece of metal is immersed in an electrolyte such as seawater,
corrosion will proceed. This means corrosion cells do exist on the surface
which involves anodic and cathodic areas
 Definitions:
 Grain: a portion of a solid metal in which atoms are arranged in an orderly pattern
(e.g. unit cells)
 Grain boundary: The irregular junction of two adjacent grains
Corrosion of Same Metal
 The question now is: Why would a piece of a metal or alloy have anodic as
well as cathodic areas ? The answer: There are many factors that create such
areas on the same metal surface. Some of these factors are:
 Macroscopic Factors
 Microscopic Factors
 Metallurgical Factors
Macroscopic Factors
Salt Concentration Differences
 If different parts of the same metal are exposed to different salt
concentration ionic activities, a concentration cell will form. The parts in
contact with lower salt concentration ionic activity are the anodes, while the
other parts are the cathodes.
Oxygen Differences
 If parts of the same metal are exposed to different oxygen concentration, an
oxygen concentration cell (or differential aeration cell) will form. The parts in
contact with less oxygen concentration are the anodes, while the other parts
are cathodes. Oxygen concentration cell can be caused by crevices, lap
joints, dirt and debris, moist insulation, slim deposits.
Macroscopic Factors
Temperature Differences
 If parts of the same metal are exposed to one temperature and the other
parts to a second temperature, differential temperature cells will form. In
general, the parts at the higher temperature are anodes. The parts at the
lower temperature are the cathodes.
Dissimilar metals
 When two single phase metals are in contact, such as iron and zinc, or gold
and nickel. The more noble metal will be the cathode. The other metal will
be the anode and suffer corrosion.
Microscopic Factors
Breakage of Protective Films
 Protective films are generally responsible for the corrosion resistance to
metals and alloys. The films could be invisible such as films on aluminum
alloys and stainless steels. The films could be visible such as rust on steels
and irons. The breakage of such films results from:
 High velocity of the environment. Specially if the environment is loaded with
solid particles or gaseous bubbles.
 Environment containing appreciable concentration of aggressive ions of Cl - or
Br-, or combination of Cl- and Fe+2, Cu+2 etc.
External Stresses
 A metallic structure supporting different stresses at different points has
anodic areas and cathodic areas. If all other conditions are identical, the
parts supporting the higher stress are anodic (corrode). A good example of
this is the higher tendency of tubes and pipes to corrode at the bended parts
more than in the straight parts.
Metallurgical Factors
 All commercial metals and alloys are not homogenous. They contain
impurities, inclusions, precipitates, defects and may be several phases. This
inhomogeneity produces metals and alloys with lower mechanical and
corrosion characteristic. Some metallurgical factors are:
 Points Defects

Point defects in a crystalline structure

Metallurgical Factors
 Impurities
These impurities and inclusions are particles of foreign matter embedded in the solid,
In acidic environment some of these impurities and inclusions will be anodic areas and
create micro galvanic cells which will cause metals to corrode.

 Vacancies
They are caused by the absence of atoms in the crystal due to non equilibrium fast
cooling rate, or cold work.

 Voids
They are holes within the material. Causes:
 Entrapment of air.
 Release of gas during casting
 Presence of trace amount of moisture which turn to steam when contacted to hot liquid
metal
 Shrinkage during solidification
Metallurgical Factors
 Line Defects (Also called dislocations)
They occur when planes of atoms rather than individual atoms are not perfectly
fitted into the lattice. There are two types of dislocations: Edge and Screw

Two types of dislocation in crystal lattices:

(a) Edge dislocation (b) Screw dislocation
Metallurgical Factors
 Tips, Sharp corners, Edges and Grain boundaries
Tips and sharp corners are more reactive than edges, while edges are more reactive than
surfaces.

 Cracks
They are caused during casting, usually as a result of uneven rates of cooling. They can also
be created during forging and are very common near weldments.

 Residual Tensile Stresses (RTS)

RTS results from fabrication processes such as deep drawing, punching, rolling, mismatch in
riveting, spinning, cold worked welding, and improper cooling from high temperatures.
Stressed areas are anodic areas.

 Multiphase alloy
They are formed by a metal alloy composed of multiple phases such as stainless steel, cast
iron, or aluminum alloy. The individual phases possess different electrode potentials phase
resulting in one act as an anode and subject to corrosion
Metallurgical Factors
 Precipitation
Precipitation is the formation of intermetalics (intermediate constituents). They
are species formed from metal atoms and having identifiable chemical formula.
Improper heat treatment (e.g., sensitization of austenitic stainless steels) will
result in the precipitation of intermetalics at the grain boundaries.

Effect of precipitate due to sensitization of type 304 stainless steel

Metallurgical Factors
 Precipitation
The presence of precipitates with minor alloying elements and impurities can
lead to corrosion problems. The precipitation of nitrides or carbides along the
grain boundaries of the stainless steel can result in depletion of chromium (Cr) in
regions surrounding the precipitated particles. These Cr- depleted regions are
anodic to the adjacent cathodic matrix and corrode.
The precipitates are generated by wrong heat treatment such as welding or by
long term thermal exposure.
Closing note
 All the above factors will induce (microscopic) anodic and cathodic areas on
the metal. The interfaces (grain boundaries) among the anodic and cathodic
areas are the contact paths that allow the transfer of electrons
Examples on Corrosion of Same Metal
 Example 1
Excess of carbon than the solubility limits in carbon steel will produce two phases; ferrite and
cementite (Fe3C). Fe3C is more noble (cathode) to ferrite.
 Example 2
Graphite flakes in cast iron are more noble (cathode) to ferrite (anodes).
 Example 3
Zinc (anode) containing some impurity atoms of more noble metals (cathode) metals such as Cu, Fe,
Ni…..etc.
 Example 4
Retained impurities, from the original extractive processes of iron, produce inclusions.The important
inclusions are iron sulfide (FeS), iron phosphate (Fe3P), and MnS which are noble to ferrite.
 Example 5
Precipitation of chromium carbide, (FeCr) 23C6, at the grain boundaries in austenitic stainless steels
(e.g. slow cooling of 300 series S.S. through the 760 to 427oC temperature range will lead to such
precipitation). This heat treatment effect of austenitic stainless steels is called sensitization.
 Example 6
Precipitation of (CuAl2) and in some aluminum alloys (FeAl3), are both anodic but Mg5Al8 and
MgZn3, both are cathodic. These precipitations are a result of aging treatment.
 Examples on Corrosion of Same Metal
 Example 7: Effect of Inclusions
Inclusions are particles of foreign material in a
(a)
metallic matrix. The particles are usually compounds
(such as oxides, sulfides, or silicates).
When inclusions at the metal surface exposed to a
corrosive environment, they can affect corrosion
behavior. The effects of inclusions are shown in the
figure, which represents an inclusion on the metal
surface prior to corrosion. Fig(b) indicates if the
inclusion is active (anodic to the rest of the metal
surface), then inclusion dissolves and leaves a hole or a
pit. Fig 2.7(C) indicates if only portions of the inclusion (b) (c)
are active, then these active portions are attacked
leaving pits.
Fig(d) indicates if the inclusion is noble (cathodic to
the rest of the surface), then accelerated attack of the
surface adjacent to the noble inclusion will occur
creating crevices between the inclusion and the (d) (e)
adjacent surfaces. Example of an inclusion is
manganese sulfide (MnS).
 Case History
 Case History 1
An explosion and fire that destroyed an entire chemical plant was traced to the
welding of galvanized steps to the side of a storage tank. The cause is:
The weld was contaminated with Zinc. All grain boundaries around the weld became
loaded with zinc, which caused inter-granular corrosion (IG) at high rates. Note the
melting point of Zn is 419.4oC.
 
 Case History 2
Stainless steel heat exchanger tubes were softened with a propane torch flame to
bend them. Within a few weeks of operation, all tubes failed at the bends. The cause
is:
The tubes were charged with carbon from the propane, plus heating in the critical
temperature range of sensitizing (500 to 850oC)