CORROSION AND

CONTROL
Prepared by Sicily Tiu
 TABLE
of contents

Oxidation and Reduction Electrochemical

Reactions
Galvanic Couple
Standard Half-Cell
Standard Hydrogen Electrode
Metal Oxidation Rate
Two Types of Polarization
Nature of Deteriorative Process
Material Deterioration
All materials experience interactions with various environments
that can impair their mechanical, physical, or aesthetic properties.
Ignoring material degradation can lead to design failures.

Deteriorative Mechanisms
Metals
Degrade by corrosion (material loss through dissolution or
oxidation).
Ceramics
Highly resistant but deteriorate under extreme conditions (high
temperatures, corrosion).
Polymers
Deteriorate via degradation (dissolving in solvents, UV or heat-
induced molecular changes).

Prevention and Mitigation

Focus on understanding the environmental impact on each
material type to implement preventive measures.
Corrosion of Metals
Destructive, unintentional attack on a metal, typically
electrochemical in nature.
Affects both the economy and everyday structures (e.g., rust on
cars, radiators).
Approximately 5% of industrialized nations' income is spent on
corrosion-related issues.

Corrosion Prevention
Understanding these reactions is crucial for developing prevention
strategies like coatings, inhibitors, and materials engineering.
Electrochemical Mechanism

Oxidation Reaction Reduction Reaction

(Anode) (Cathode)

Metal atoms lose electrons Electrons from oxidation reduce other

This process occurs at the anode, leading species
to metal ion formation.
Electrode Potential and Reactions
Not all metals oxidize (corrode) equally.
In a galvanic couple, two metals are connected in a liquid electrolyte, leading to one
metal (anode) corroding, while the other (cathode) undergoes reduction.
Example : Iron and Copper in a galvanic cell
Oxidation

Reduction

Copper deposits while iron corrodes (potential = 0.780 V).

Galvanic Cell and Voltage

Voltage between metals is a measure of the driving force for electrochemical reactions.
Example 2: Iron and Zinc in a galvanic cell:
Zinc corrodes, iron electrodeposits (potential = 0.323 V).

Standard Half-Cell
A pure metal electrode in a 1M solution at 25°C (77°F).
Different metal pairs produce varying voltages in such cells, reflecting their oxidation
tendencies.
 The Standard EMF Series
STANDARD HYDROGEN EMF SERIES
ELECTRODE (SHE)
Generated by coupling various metal half-
Used as a reference for comparing metal cells to the standard hydrogen electrode.
half-cells. Ranks metals based on their electromotive
Consists of platinum in a 1 M H^(+) solution force (emf), from noble (less reactive) to
with hydrogen gas at 1 atm and 25°C. highly active (more susceptible to oxidation).
Platinum acts as an inert surface for Metals like gold and platinum are chemically
hydrogen oxidation or reduction. inert, while sodium and potassium are highly
reactive.

CORROSION AND CELL POTENTIAL

In a galvanic couple, the metal lower in the

series undergoes oxidation (corrodes), while
the higher one undergoes reduction.
For a reaction to occur spontaneously, the
overall potential difference (ΔV^(0)) must be
positive.
 The Standard EMF Series
GENERALIZED REACTIONS SPONTANEITY OF REACTION

Oxidation of metal M1 (Anode) For the reaction to occur spontaneously, ΔV0​

must be positive.
Reduction of metal M2 (Cathode) If ΔV0 is negative, the reaction proceeds in
the reverse direction.
V0​ represents standard electrode potentials
from the EMF series.

OVERALL CELL REACTION CORROSION IMPLICATION

The combined reaction is The metal lower in the EMF series undergoes
oxidation (corrosion).
The overall cell potential (ΔV0​) is The metal higher is reduced.
 The Standard EMF Series

The voltages in Table above are for the half-reactions as reduction reactions, with the electrons on the
left-hand side of the chemical equation; for oxidation, the direction of the reaction is reversed and the
sign of the voltage changed.
 INFLUENCE OF CONCENTRATION AND
TEMPERATURE ON CELL POTENTIAL
IDEAL CONDITIONS AND THE EMF SIMPLIFICATION AT 25°C
SERIES
At 25°C and for 1 M concentrations, the equation simplifies to:
The EMF series is based on idealized conditions:
pure metals, 1 M ion solutions, and 25°C.
Real-world conditions differ, altering the cell
potential and possibly reversing the
spontaneous reaction direction.

NERNST EQUATION EFFECT ON SPONTANEITY

To account for changes in temperature and ion concentration, the For a reaction to be spontaneous, ΔV must
cell potential (ΔV) is determined using the Nernst equation: remain positive.
Deviations from ideal conditions can influence
reaction spontaneity.
Where:
R = gas constant., T = absolute temperature., n= number of
electrons., F = Faraday constant (96,500 C/mol).
Galvanic Series
The Galvanic Series ranks metals and alloys based on their
reactivity in seawater, a more practical comparison than the
standard EMF series.
Metals near the top of the series are cathodic (less reactive), while
those near the bottom are anodic (more reactive).

Reactivity in the Galvanic Series

Cathodic (Unreactive) metals include noble metals like gold and
platinum.
Anodic (Reactive) metals include base metals such as zinc and
magnesium.

Practical Applications
Useful for understanding corrosion behavior in real environments,
like seawater.
No voltages are provided, unlike the EMF series.
 CORROSION RATES
Corrosion rates are critical for evaluating how quickly materials degrade in real-world environments. The half-cell
potentials in the electrochemical series indicate the driving force for corrosion but do not directly measure how
fast a material corrodes.

Limitations of Half-Cell Potentials

Half-cell potentials represent equilibrium conditions and
provide no information on actual corrosion rates. In real
scenarios, systems are not at equilibrium, and there is
electron flow (current) between anode and cathode.

Corrosion Penetration Rate (CPR)

CPR quantifies the rate of material loss due to corrosion, Where:
expressed in units of mils per year (mpy) or millimeters W = weight loss over time ttt
per year (mm/yr). ρ = density of the material
The formula for CPR is: A = exposed surface area
K = constant depending on unit system
(534 for mpy, 87.6 for mm/yr)
 CORROSION RATES
A corrosion rate of less than 20 mpy (0.50 mm/yr) is generally considered acceptable for most engineering
applications.

CPR Calculation Units

In mpy: Weight loss in milligrams, density in grams per
cubic centimeter, area in square inches, and time in hours.
In mm/yr: Weight loss in milligrams, density in grams per
cubic centimeter, area in square centimeters, and time in
hours.

Corrosion Rate from Current Density

Corrosion can also be related to the current density (iii) in Where:
the system. The rate rrr (in mol/m²-s) is calculated as: i = current density (current per unit area)
n = number of electrons per ionization
reaction
F = Faraday's constant (96,500 C/mol)
PREDICTION OF CORROSION RATES
Polarization
The displacement of electrode potential from its
equilibrium value in an electrochemical reaction. Low Reaction Rate / High H⁺
This displacement is called Overvoltage (η) and is
Concentration
measured in volts or millivolts.
Adequate supply of H⁺ ions near the
Active Polarization electrode interface.
No diffusion limitation.
Reaction rate is controlled by the slowest step in a
sequence.
An activation energy barrier limits this slowest step. High Reaction Rate / Low H⁺
Concentration
Concentration Polarization Depletion zone forms near the electrode.
Occurs when the rate of mass transport (diffusion) of Diffusion of H⁺ ions to the interface becomes
ions limits the reaction. the rate-controlling step.
Controlled by ion concentration gradients.
PREDICTION OF CORROSION RATES

Passivity Forms of Corrosion

Metals like chromium, iron, nickel, and aluminum, Corrosion can be classified into eight primary
under certain conditions, lose chemical reactivity and forms:
become inert due to the formation of a thin Uniform Corrosion
protective oxide film. Galvanic Corrosion
Crevice Corrosion
Environmental Effects Pitting Corrosion
Factors like fluid velocity, temperature, and corrosive Intergranular Corrosion
concentration influence corrosion rates. Selective Leaching
Increased fluid velocity or temperature typically Erosion-Corrosion
raises corrosion rates. Stress Corrosion Cracking
Higher corrosive concentration can either
increase corrosion or cause metals capable of Uniform Attack
passivation to form protective films. A form of electrochemical corrosion that
occurs uniformly over the entire exposed
surface.
 PREDICTION OF CORROSION RATES
Galvanic Corrosion Pitting
Occurs when two metals or alloys with different A localized form of corrosion characterized by the
compositions are electrically coupled in an formation of small pits or holes.
electrolyte. Mechanism
Mechanism Similar to crevice corrosion; oxidation occurs
The less noble (more reactive) metal experiences within the pit, while reduction takes place at the
corrosion. surface.
The more inert metal acts as a cathode and is Gravity influences downward growth,
protected. concentrating the solution at the pit tip.
Crevice Corrosion Intergranular Corrosion
Electrochemical corrosion resulting from Corrosion that occurs preferentially along the grain
concentration differences of ions or dissolved gases boundaries of certain alloys.
in stagnant electrolyte solutions. Mechanism
Mechanism Sensitization occurs when stainless steels are
Occurs in areas with lower ion concentration. heated to temperatures between 500°C and
Common in crevices, recesses, or under deposits 800°C (950°F and 1450°F) for extended periods.
where dissolved oxygen is depleted.
 PREDICTION OF CORROSION RATES
Selective Leaching
A corrosion process occurring in solid solution alloys Stress Corrosion
where one element is preferentially removed. Also known as stress corrosion cracking, this
Effects phenomenon occurs due to the combined effects of
Significant impairment of the mechanical applied tensile stress and a corrosive environment.
properties of the alloy. Mechanism
Color change from yellow to red or copper as Small cracks form and propagate perpendicular
zinc is removed. to the applied stress, leading to failure that
resembles brittle fracture, even in ductile
Erosion Corrosion materials.
A type of corrosion resulting from the combined
Cracks can develop at low stress levels, below
effects of chemical attack and mechanical abrasion
the material's tensile strength.
due to fluid motion.
Most alloys are vulnerable in specific environments:
Virtually all metal alloys are affected, particularly
Stainless steels: Susceptible in chloride ion
those that form protective surface films. The
solutions.
abrasive action can erode this film, exposing bare
Brasses: Vulnerable when exposed to ammonia.
metal.
PREDICTION OF CORROSION RATES
Hydrogen Embrittlement
A phenomenon in which certain metal alloys, particularly some steels,
experience a reduction in ductility and tensile strength when atomic
hydrogen (H) penetrates into the material.
Mechanism
Hydrogen diffuses interstitially through the crystal lattice, causing
brittle fracture under applied or residual tensile stresses.
Concentrations as low as parts per million can initiate cracking, often
resulting in transgranular cracks, though intergranular fractures may
occur in some alloys.
Distinction from Stress Corrosion
Both phenomena involve tensile stress and a corrosive environment
but differ in their responses to electric currents:
Stress Corrosion: Reduced by cathodic protection.
Hydrogen Embrittlement: Can be initiated or enhanced by
cathodic protection.
PREDICTION OF CORROSION RATES
Cathodic Protection
A corrosion prevention technique that can effectively combat all forms of corrosion by
supplying electrons to a metal, converting it into a cathode and reversing the oxidation
reaction.
Mechanism
Generalized Reaction:

Techniques:
Galvanic Protection
Involves connecting the protected metal to a more reactive metal (sacrificial anode).
Common materials: Magnesium and Zinc.
Impressed Current
Uses an external DC power source to provide electrons.
The negative terminal connects to the metal structure, while the positive connects to
an inert anode (e.g., graphite) buried in soil.
A current path completes the circuit through the soil, enhancing protection.
 PREDICTION OF CORROSION RATES

Scale Types
The rate of oxidation and the protective ability of an Interpretation:
oxide film on metals are influenced by the relative P–B Ratio < 1: The oxide film is porous and
volumes of the oxide and the metal. unprotective.
Pilling–Bedworth (P–B) Ratio: P–B Ratio = 1: The oxide film is stable and
The P–B ratio helps determine the protective protective.
nature of an oxide film formed during oxidation. P–B Ratio > 1: The oxide film is dense and
protective.
Alternative Expression for Other Metals:
Where: For divalent metals, the P–B ratio can be
A0= Molecular (or formula) weight of the oxide expressed as:
AM= Atomic weight of the metal
ρO = Density of the oxide
ρM​= Density of the metal Where a is the coefficient of the metal species for
the overall oxidation reaction.
PREDICTION OF CORROSION RATES

Corrosion of Ceramic Materials Chemical Reaction Effects

Ceramics are compounds formed between Chemical Agents
metallic and nonmetallic elements, inherently Oxygen and Ozone (O₃) can accelerate the
more resistant to corrosion due to their stable degradation of vulcanized rubbers,
structure. particularly those with double bonds in their
Corrosion Resistance molecular chains.
Ceramics exhibit exceptional immunity to Chain Scission
corrosion in most environments, especially Ozone-induced chain scission occurs when
at room temperature. ozone reacts with the double bonds,
Corrosion mechanisms typically involve severing the molecular chains and leading to
simple chemical dissolution, contrasting material degradation.
with the electrochemical processes seen in In unstressed states, an oxide film can form on
metals. the rubber surface, providing protection against
further degradation.
PREDICTION OF CORROSION RATES

Thermal Effects Weathering

Thermal Degradation Weathering refers to the degradation of
Occurs due to the scission of molecular polymeric materials due to exposure to outdoor
chains at elevated temperatures. conditions.
Results in chemical reactions that produce Causes of Weathering
gaseous byproducts, leading to weight loss Primarily caused by oxidation initiated by
in materials. ultraviolet (UV) radiation from sunlight.
Thermal Stability Water Absorption
A measure of a polymer's resilience against Polymers like nylon and cellulose can
decomposition. absorb water, leading to decreased
The stability is influenced by bond strengths: hardness and stiffness.
C—F bonds (in fluorocarbons) are
stronger than C—H bonds, which are
stronger than C—Cl bonds.
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