CORROSION OF

METALS AND ALLOYS

TRACK SPECIALIZATION 3

GROUP 3
BACABAC | DE CASTRO | GALAGAR
 TYPES OF
METALLIC CORROSION
 UNIFORM CORROSION

It is generally thought of as metal

loss due to chemical attack or
dissolution of the metallic
component into metallic ions.

In high-temperature situations,
uniform metal loss is usually
preceded by its combination with
another element rather than its
oxidation to a metallic ion.
 UNIFORM CORROSION

A metal resists corrosion by

forming a passive film on the
surface.

The immunity of the film to

attack is a function of
the film composition,
temperature, and the
aggressiveness of the chemical.
 INTERGRANULAR CORROSION

This is a specialized type of

attack that takes place at the
grain boundaries of a metal.

This results in the flow of energy

from the small anode area to the
large cathode area, which
causes rapid attack penetrating
deeply into the metal
 INTERGRANULAR CORROSION

The following factors contribute to the increased

reactivity of the grain boundary areas:

1. Segregation of specific elements or compounds

2. Enrichment of one of the alloying elements at the
grain boundary
3. Depletion of the corrosion-resistant element at the
grain boundary
 GALVANIC CORROSION

Dissimilar metal corrosion/

bimetallic corrosion

When two different metallic

materials are electrically
connected and placed in a
conductive solution (electrolyte),
an electric potential exists.
 GALVANIC CORROSION

• Chloride concentrations are high, a change to the

active state will usually take place
• Oxygen starvation also causes a change to the active
state.
• Ideally, the anodic area should be larger than the
cathodic area.
• Cathodes will develop at high oxygen concentrations,
and anodes will develop at points of low oxygen
concentration.
GALVANIC CORROSION
 CREVICE CORROSION

Crevice corrosion is a
localized type of corrosion
occurring within or adjacent
to narrow gaps.

Crevice corrosion in any

corrosive environment,
especially in seawater.
 PITTING CORROSION

It is characterized by a highly
localized loss of metal. The
initiation of a pit is associated with
the breakdown of the protective
film on the metal surface.

The depth of a pit eventually leads

to a through penetration or a
massive undercut of the thickness
of a metal part.
 PITTING CORROSION

Concentration cells - areas of the same metal where

oxygen or conductive salt concentrations in water differ.
 EROSION CORROSION

Erosion corrosion is
usually caused by an
aqueous or gaseous
corrodent flowing over
the metal surface or
impinging upon it.
 EROSION CORROSION
It is affected by velocity,
turbulence, impingement, the
presence of suspended solids,
temperature, and prevailing
cavitation conditions.
Fretting corrosion is when two
metal surfaces are in contact
and experience a very slight
relative motion that results in
damage to one or the other
surfaces
 STRESS CORROSION CRACKING

SCC is defined as the delayed

failure of alloys by cracking
when exposed to certain
environments in the presence
of static tensile stress.
 STRESS CORROSION CRACKING
The rate of propagation can vary
greatly and is affected by stress
levels, temperature, and
concentration of the corrodent.
The conditions necessary for
stress corrosion are:
1. Suitable environment
2. Tensile stress
3. Sensitive metal
4. Appropriate temperature and
pH values
 BIOLOGICAL CORROSION

Biologically influenced corrosion

refers to the degradation of
metals caused by the activity of
living organisms. This is also
referred to as microbial-induced
corrosion (MIC).
 BIOLOGICAL CORROSION

• Produce a corrosive environment

• Create electrolytic cells on the
metal surface
• Alter the resistance of surface
films
• Have an influence on the rate of
anodic or cathodic reactions
• Alter the environmental
composition
 BIOLOGICAL CORROSION

The methods by which microorganisms increase the rate of

corrosion of metals and/or their susceptibility to localized
corrosion in an aqueous environment are:

1. Production of metabolites
2. Destruction of protective layers
3. Hydrogen embrittlement
4. Formation of concentration cells at the metal surface
5. Modification of corrosion inhibitors
6. Stimulation of electrochemical reactors
 SELECTIVE LEACHING

Dezincification is the term used

to describe the leaching of zinc
from brass.

Low zinc alloys favor plug type

while layer-type attack is more
prevalent in high-zinc alloys.
 SELECTIVE LEACHING

Plug-type attack is found in

neutral or alkaline water, high
salt content, and above room
temperatures.

Uniform attack takes place in

slightly acidic water, low salt
content, and at room
temperature
 SELECTIVE LEACHING

Graphite corrosion is the term used to describe the selective

leaching of iron from gray cast iron.

Conditions that favor selective leaching are:

1. High temperatures
2. Stagnant solutions, especially if acidic
3. Porous inorganic scale formation
 HYDROGEN DAMAGE

The hydrogen may be initially

present in the metal or it may
accumulate through absorption.
In most cases, the damage is
associated with residual or
applied stresses.
 HYDROGEN DAMAGE

The damage may be in the form of:

1. Loss of ductility and tensile strength
2. Sustained propagation of defects at
stresses well below those required
for mechanical failure
3. Internal damage due to defect
formation
4. Macroscopic damage, such as
internal flaking, blistering, fissuring,
and cracking
 LIQUID METAL ATTACK
The most drastic form of liquid metal attack is the
instantaneous fracture of the solid metal in the presence of
stress, a condition described as “liquid metal embrittlement”

The general requirements for LME to occur in a ductile metal

are as follows:
1. There must be a wetting or intimate contact of the solid
metal by the liquid metal.
2. The solid metal must be stressed to the point of producing
plastic deformation.
3. There must be an adequate supply of liquid metal.
 EXFOLIATION
When intergranular corrosion
takes place in a metal with a
highly directional grain structure,
it propagates internally, parallel
to the surface of the metal.

Exfoliation requires elongated

(parallel-shaped) grains, a
susceptible grain
boundary condition, and a
relatively severe environment
 CORROSION FATIGUE
Corrosion fatigue is the cracking of a
metal or alloy under the combined
action of a corrosive environment and
repeated or fluctuating stress.

Corrosion fatigue can be defined as

the reduction in fatigue life of a metal
in a corrosive environment.

Fatigue failure is when metals and

alloys fail by cracking when subjected
to cyclic or repetitive stress.
 FILIFORM CORROSION
Metals with semipermeable
coatings or films may undergo a
type of corrosion resulting in
numerous meandering threadlike
filaments of corrosion beneath
the coatings or films

If an advancing head meets

another filament, it gets diverted
and starts growing in another
direction.
 FILIFORM CORROSION

The growth formation is explained by the

formation of a differential aeration cell
CORROSION MECHANISM
AND KINETICS
 Corrosion Mechanism

Corrosion by its simplest definition is the process of a metal returning to

the material’s thermodynamic state.

The location where electrons are being given up are identified as anodes.

The sites where electrons are being absorbed are denoted as cathodes.

A difference in electrical potential exists between these two areas

and a complete electrical circuit develops.
 Corrosion Mechanism
The faster the dissolution of the metal (rate of corrosion), the higher the
current flow.

A corroding metal does not accumulate any charge.

 Cell Potential

Reaction will occur only if there is a negative free energy change (ΔG)

∆𝐺 = −𝑛𝐹𝐸

For a given reaction to take place, the cell potential is taken as the
difference between the two half-cell reactions

𝐸 = 𝐶𝑎𝑡ℎ𝑜𝑑𝑒 ℎ𝑎𝑙𝑓 𝑐𝑒𝑙𝑙 − 𝐴𝑛𝑜𝑑𝑒 ℎ𝑎𝑙𝑓 𝑐𝑒𝑙𝑙

 Types of Local Cell Formation
DISSIMILAR ELECTRODE CELLS

Dissimilar electrode cells may be

formed when two dissimilar metals
are in contact or due to the
heterogeneity of the same metal
surface

This is often referred to as galvanic

coupling, in which the less noble
metal becomes the anode
 Types of Local Cell Formation
CONCENTRATION CELLS

Concentration cells are formed

when the electrodes are identical
but are in contact with solutions of
differing composition

A salt concentration cell forms

when one electrode is in contact
with a concentrated solution and
the other electrode with a dilute
solution
 Types of Local Cell Formation
CONCENTRATION CELLS

A differential aeration cell forms

when the identical electrodes are
exposed to solutions of identical
chemical composition that differ in
oxygen content.

The electrode in contact with the

less aerated or oxygenated
solution will act as the anode
 Types of Local Cell Formation
DIFFERENTIAL TEMPERATURE CELL

Formed when electrodes of the

same metal, each of which is at a
different temperature, are
immersed in an electrolyte of the
same initial composition

Polarity developed in an electrode

varies from system to system
 Types of Local Cell Formation
METAL ION CONCENTRATION CELLS

This situation arises when a

significant difference in metal ion
concentration exists over a metal
surface

An electrical potential exists between

the two points: the area of the metal in
contact with the low concentration of
metal ions is anodic and corrodes
 Types of Local Cell Formation
OXYGEN CONCENTRATION CELLS
An oxygen cell can develop at any
point where the oxygen in the air is
not allowed to diffuse into the
solution, thereby creating a
difference in oxygen concentration
between two points.

Corrosion occurs at the area of low

oxygen concentration (anode). Alloys
such as stainless steel are particularly
susceptible to this type of crevice
corrosion.
 Potential-Ph Diagrams

Also known as Pourbaix Diagram

Graphical representation of metal

stability and corrosion products

Constructed from calculations

based on the Nernst equation and
the solubility data for various
metal compounds
 Pourbaix Diagram

Horizontal lines: Pure electron

transfer reactions that is
dependent only on potential

Vertical lines: Doesn’t involve

electron transfer and is only
dependent on pH

Sloping lines: Equilibria

involving both electron
transfer and pH
 Pourbaix Diagram
Immunity Zone. Under these condition
of potential and pH, the metal remains
in metallic form and is free from
corrosion

Corrosion Zone. Under these condition

of potential and pH, the metal corrodes

Passive zone. Under these condition of

potential and pH, protective layer of the
metal's hydroxide or oxide form on iron
and further corrosion of metal doesn’t
take place
 Potential-Ph Diagrams

Uses
1. Predicting the spontaneous direction of reactions

2. Estimating the stability and composition of corrosion

products

3. Predicting environmental changes that will prevent or

reduce corrosion
 Potential-Ph Diagrams

Limitations
1. Represent equilibrium conditions and cannot predict rate of
reaction.

2. Passivity may not always be true. They may not always

precipitate on the metal surface

3. Precipitation of other ions are not considered

4. pH at the metal surface may vary drastically

 Polarization
Change in Potential of an electrode during electrolysis, when the anode’s
potential becomes nobler than that of the cathode.

Decreases output voltage of a cell, and increases voltage required for

electrolysis cells.

Caused by intermediate resistance in the circuit. Some factors affecting

resistance:
● Resistivity of the media
● Surface films
● Metal properties
 Polarization Curves

The intersection of the two polarization

lines (curves) closely approximates the
corrosion current and the combined cell
potentials from the freely corroding
situation.

Helps estimating corrosion rates and

extent or severity of the corrosion
 Polarization Curves
Polarization may occur at the cathode
or at the anode

Cathodic polarization reduces the

corrosion rate due to increased current
resistance. It is also the most common
type of polarization

Three basic causes of polarization

● Termed activation
● Concentration
● Potential drop
 Activation Polarization

Arises out of a slow step in the electrode

reaction for which an activation energy in the
form an increment in potential is required for
the reaction proceed.

1. Hydrogen ions are absorbed from the

solution onto the anode surface.
2. Electron transfer occurs from the anode to
the hydrogen ions to form hydrogen.
3. The hydrogen atoms form hydrogen gas
molecules.
4. Hydrogen gas bubbles are formed.
 Concentration Polarization

Polarization of an electrolytic cell

resulting from changes in the
electrolyte concentration due to the
passage of current through the
electrode/solution interface.

Inherent in membrane separation

processes such as:
● Gas separation
● Pervaporation
● Reverse Osmosis
 Resistance Polarization

Also known as Ohmic Polarization

The change in voltage associated

with effects of the environment and
the circuit between the anode and
cathode sites. It includes the effects
of the resistivity of the media,
surface films, corrosion products,
etc.
 Factors Affecting Corrosion
Temperature
Reaction rates increases with temperature

Velocity
Increasing the velocity of the corrodent, will increase the
corrosion rate.

When using Passive materials, increasing the velocity could

lower corrosion rates
 Factors Affecting Corrosion
Surface Finish
Rough surface or tight crevices can facilitate formation of
concentration cells

Time
Corrosion rates are expressed using a time dimension
 Corrosion Rate Measurement

Corrosion involves dissolution of metal as a result of which the metallic

part loses its mass

Most widely used expression is based on weight loss

mg/dm2/day (mdd)

Rate expression on penetration is:

inch penetration/year (ipy)

mils penetration/year (mpy)
mpy=1000* (ipy)
 Corrosion Rate Measurement
543𝑊
𝑚𝑝𝑦 =
𝐷𝐴𝑡
W = weight loss (mg)
D = density (g/cm3)
A = area of specimen (in2 )
t = exposure time (h)

1.44𝑚𝑑𝑑
𝑚𝑝𝑦 =
𝑑𝑒𝑛𝑠𝑖𝑡𝑦

𝑚𝑑𝑑 = 𝑚𝑝𝑦(0.696)(𝑑𝑒𝑛𝑠𝑖𝑡𝑦)
FACTORS AFFECTING
METAL CORROSION
 Atmospheric Corrosion

Atmospheric corrosion is a
complicated electrochemical
process taking place in
corrosion cells consisting of
base metal, metallic corrosion
products, surface electrolytes,
and the atmosphere.

It has received considerable

attention because of the
staggering costs that result.
 Atmospheric Corrosion
Variables that influence atmospheric corrosion:
● Relative humidity
● Temperature
● Sulfur dioxide content
● Chlorine content
● Amount of rainfall
● Dust
● Position of the exposed metal
 Atmospheric Corrosion

Metals corrode at a negligible rate in the absence of

moisture, which is the common electrolyte associated with
atmospheric corrosion

Rusting is negligible in climates where the air temperature

is below the freezing point of water because ice is a poor
conductor and does not function effectively as an
electrolyte.
 Factors Affecting Metal Corrosion

The usual electrolyte associated with

atmospheric corrosion is water resulting
from rain, fog, dew, melting snow, or
high humidity

Corrosion takes place only during the

time of wetness.
 Factors Affecting Metal Corrosion

1. Time of Wetness
2. Composition of the Surface Electrolyte
3. Temperature
4. Initial Exposure
5. Wind Velocity
6. Nature of Corrosion Products
7. Pollutants Present
 Factors Affecting Metal Corrosion

1. Time of Wetness

Time of wetness refers to

the length of time during
which the metal surface is
covered by a film of water
 Factors Affecting Metal Corrosion

1. Time of Wetness
It depends on the:
● Relative humidity of the atmosphere:
● Temperature of the air and the metal surface above 0°C
● The duration and frequency of rain, fog, dew, and
melting snow;
● Hours of sunshine and wind speed.
 1. Time of Wetness
Adsorption Layers
The amount of water adsorbed on a
metal surface depends on the relative
humidity of the atmosphere and on the
chemical and physical properties of the
corrosion products.
For such adsorption to take place, the
relative humidity must be above a
certain relative value known as the
critical relative humidity
 1. Time of Wetness
Phase Layers
Dew
● occurs when the temperature of the metal surface is below the
dew point of the atmosphere.
Rain
● Rain creates even thicker layers of electrolyte on the surface than
dew
● It affects corrosion by adding a phase layer of moisture and
corrosion stimulators
 1. Time of Wetness
Phase Layers
Fog
● high acidity and high
concentrations of sulfates and
nitrate can be found in fog droplets
in areas of high air pollution.
Dust
● Dust can promote corrosion
because of their hygroscopic
nature
 Factors Affecting Metal Corrosion

2. Composition of the Electrolyte

Some known pollutants:
The electrolyte film on the
surface will contain various ● Oxygen
species deposited from the ● SOx
atmosphere or originating
from the corroding metal. ● NOx
● Chlorides
● CO2
 Factors Affecting Metal Corrosion

3. Temperature

During long-term exposure in a temperate climatic zone ,

the temperature appears to have little or no effect on the
corrosion rate.

As the temperature increases, the rate of corrosive attack

will increase as a result of an increase in the rate of
electrochemical and chemical reactions as well as the
diffusion rate.
 Factors Affecting Metal Corrosion

3. Temperature

Conversely, an increase in temperature can cause a

decrease in the corrosion rate by causing a more rapid
evaporation of the surface moisture film.

In addition, as the temperature increases, the solubility

of oxygen and other corrosive gases in the electrolyte
film is reduced.
 Factors Affecting Metal Corrosion

4. Initial Exposure
Atmospheric corrosion rates proceed through three stages
or periods:

Induction Period

The metal is covered with a spontaneously formed oxide and

aqueous layer.
 Factors Affecting Metal Corrosion

Transition Period
The oxide layer transforms into a fully developed layer of
corrosion products.

Stationary Period

The surface being fully covered by corrosion product and

reach constant corrosion rate.
 Factors Affecting Metal Corrosion
5. Wind Velocity

Wind speed and type of wind flow have pronounced effects

on the atmospheric corrosion rate.

This is illustrated by the dry deposition velocity, which is

defined as the ratio of deposition rate of any gaseous
compound and the concentration of that compound in the
atmosphere.
 Factors Affecting Metal Corrosion
6. Nature of Corrosion Products

Atmospheric corrosion rate is influenced by the formation

and protective ability of the corrosion products formed.

The eventual thickening of the film of corrosion products can

be described in a sequence of consecutive steps:
dissolution → coordination → reprecipitation
 Factors Affecting Metal Corrosion
6. Nature of Corrosion Products
The corrosion products formed are the composition of the
metal or alloy and the contaminants present in the
atmosphere.

Initiation of corrosion is the result of the presence of solid

particles on the surface.

Greater corrosive effects result when particles of hygroscopic

salts settle on the surface and form a corrosive electrolyte.
 Factors Affecting Metal Corrosion
6. Nature of Corrosion Products
When small amounts of copper,
chromium, nickel, etc. are added to
carbon steel, low-alloy carbon steel
results. These steels are known as
weathering steels.

The corrosion rate becomes stabilized

within 3 to 5 yr. A dark brown to violet
patina develops over this period.
 Factors Affecting Metal Corrosion
7. Pollutants Present

One of the most The following gaseous constituents

important factors contribute to atmospheric corrosion:
affecting ● O2 ● HNO3
atmospheric
corrosion is the ● H2O2 ● NH3
presence of specific ● SO2 ● HCl
pollutants.
● H2S ● HCHO
● COS ● HCOOH
● NO2
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