Introduction to

Corrosion What is Corrosion?

Corrosion Chemistry
Corrosion Control
PRT 110
Introduction to Petroleum
Refining
 WHAT IS
CORROSION?

Introduction to Petroleum Refining

 Corrosion
the deterioration of a material (usually a metal)
or its properties because of a reaction with its
environment

Why do metals corrode?

to return the absorbed and stored energy
required to release the metals from their original
compounds

Introduction to Petroleum Refining

 Factors Affecting Corrosion Resistance of a Material

Metallurgical Environmental Protective

Factors Factors Treatments

Corrosion
Resistance

Mechanical
Application Safety Factors Properties

Introduction to Petroleum Refining

 Types of Corrosion
Type Characteristics Examples
Uniform •All areas of the metal corrode at the Oxidation and tarnishing;
same rate active dissolution in acids;
•Unsightly but typically takes a long atmospheric and immersed
time to progress to failure corrosion
•Easiest to mitigate because of its
high visibility and slow progress
Localized •Certain area corrode at a higher rate Crevice corrosion; pitting
than others due to heterogeneities in corrosion; deposit attack;
the metal, the environment or in the weld decay
geometry of the structure

Introduction to Petroleum Refining

 Types of Corrosion

Introduction to Petroleum Refining

 Types of Corrosion

Introduction to Petroleum Refining

 Localized Corrosion
• Pitting Corrosion

• Very destructive due to the depth of corrosion

and its tendency to go unnoticed
• Frequently results in perforation of the metal
with consequent leakage
• Can be caused by flaws in protective coating, wet
thermal insulation or stray current from a
cathodic protection system
• Control: avoid presence of crevices, deposits and
stagnant volumes of solutions

Introduction to Petroleum Refining

 Localized Corrosion
• Pitting Corrosion

Introduction to Petroleum Refining

 Localized Corrosion
• Crevice Corrosion
• Very destructive due to its ability quietly cause
damage deep inside a material, usually out of sight

• Characterized by a geometric configuration in which

the cathode reactant (usually dissolved oxygen) can
readily gain access by convection and diffusion to the
metal surface outside the crevice, whereas access to
the layer of the stagnant solution within the crevice is
far more difficult and can be achieved only by
diffusion through the narrow mouth of the crevice

Introduction to Petroleum Refining

 Localized Corrosion
• Crevice Corrosion (Formation)

• Geometry of structure
– riveted plates
– welded fabrication
– threaded joints
• Contact of metal with non-metallic
solids
– plastics, rubber, glass
• Deposits of sand, dirt or permeable
corrosion products on the metal
surface (“deposit attack”)
Introduction to Petroleum Refining
 Localized Corrosion
• Crevice Corrosion (Control)

• Design: avoid crevices and geometric conditions that lead to the

formation of deposits on the metal surface
• Welded butt joints should be used in preference to riveted or bolted
joints
• Crevices should be sealed by welding, soldering, or by use of caulking
compounds
• Solids should be removed from process liquors or vessels should be
designed so that deposition of solids does not occur (avoid sharp
corners and stagnant areas by providing facilities for complete
drainage of the process liquor)
• Use non-absorbent materials in gaskets

Introduction to Petroleum Refining

 Localized Corrosion
• Galvanic Corrosion

• Occurs when two metals of different potential are coupled together

• Majority of the corrosion occurs at the interface
• Can be destructive due to its localized nature
• Factors affecting corrosion rate
q corrosion potentials of metals forming the couple under the
environmental conditions that prevail in practice
q nature and kinetics of the cathodic reaction (surface of the more
positive metal) and of the anodic reaction (surface of the more
negative metal)
q relative areas of the metals
q nature and conductivity of the electrolyte solution
Introduction to Petroleum Refining
 Localized Corrosion
• Galvanic Corrosion

• The Galvanic Series

Introduction to Petroleum Refining

 Localized Corrosion
• Galvanic Corrosion (Protective Measures)

• Prior to installation: refer to compatibility of

metals
• Reduction of area of the more noble metal
• Complete electrical insulation
• Metallic coating (Al and steel – aluminize the steel)
• Paint coating

Introduction to Petroleum Refining

 Localized Corrosion
• Conjoint Action of Corrosion and a Mechanical Factor

• Due to the synergistic action of a mechanical factor

and corrosion
• Includes fretting corrosion, cavitation damage,
stress corrosion and corrosion fatigue

Introduction to Petroleum Refining

 Localized Corrosion
• Conjoint Action of Corrosion and a Mechanical Factor
• Fretting Corrosion

• Occurs at the interface of two closely fitting surfaces

when they are subject to slight relative oscillatory slip
• Surfaces are often badly pitted and finely divided oxygen
detritus is performed
• Also called false brimelling, chafing fatigue, cocoa,
friction oxidation
• Can cause serious dimensional loss of accuracy of closely
fitted components and reduce the fatigue strength of a
machine component

Introduction to Petroleum Refining

 Localized Corrosion
• Conjoint Action of Corrosion and a Mechanical Factor
• Fretting Corrosion (Factors Affecting Amount of Damage)

Atmosphere Amplitude of slip Hardness

Temperature Number of fretting cycles Lubricant
Load Frequency of oscillation

• Fretting Corrosion (Preventive Measures)

For Surfaces Not Intended to Move For Surfaces Intended to Undergo

Relative Motion
•Eliminate source of vibration •Lower amplitude of vibration
•Increase friction between surfaces •Improve lubrication conditions

Introduction to Petroleum Refining

 Localized Corrosion
• Conjoint Action of Corrosion and a Mechanical Factor
• Cavitation Damage

• Occurs in materials in rapidly moving liquid

environment
• Cavities are formed in the liquid in regions of very low
pressure caused by flow divergence, rotation or
vibration

Introduction to Petroleum Refining

 Localized Corrosion
• Conjoint Action of Corrosion and a Mechanical Factor
• Cavitation Damage (Factors Affecting Resistance of Materials)

• Hardness
• Tensile Strength
• Resilience

• Cavitation Damage (Remedial Measures)

• Elimination of severe turbulence

• Reduction of vibration

Introduction to Petroleum Refining

 Types of Corrosion
Type Characteristic
Microbiologically-Induced •Caused by bacteria colonies (biofilm) parking
Corrosion themselves on a metal surface
•Some of the bacteria produce sulfuric acid,
others oxidize iron, leading to pitting corrosion
•Some bacteria produce biofilm that can lead to
crevice corrosion

Introduction to Petroleum Refining

 CORROSION
CHEMISTRY

Introduction to Petroleum Refining

 Atoms and Ions

Electrons

Protons

Neutrons

Introduction to Petroleum Refining

 Atoms and Ions
Atoms Ions

• smallest particle of an • charged particles

element (neutral)
+ - +3 + -
26 Fe : 26 p ; 26e 26 Fe : 26 p ; 23e
cation

+ - - + -
17 Cl : 17 p ; 17e 17 Cl : 17 p ; 18e
anion

Introduction to Petroleum Refining

 Oxidation-Reduction Reactions
Oxidation

• loss of electrons

Reduction

• gain of electrons

2 Fe( s ) + 3Cl2 ( g ) ® 2 FeCl3( s )

When ionic compounds are dissolved in water, they break up into
separate ions (ionization)

Introduction to Petroleum Refining

 Corrosion as a Chemical Reaction
• Corrosion in Acids
Zn + H 2 SO4 ® ZnSO4 + H 2 ­

• Corrosion in Neutral and Alkaline Solutions

Fe + 6 H 2O ® 3O2 + 4 Fe(OH )3 ¯
2 Fe(OH )3 ® Fe2O3 + 3H 2O

Introduction to Petroleum Refining

 Corrosion Products

soluble insoluble

Introduction to Petroleum Refining

 Electrochemical Reactions

Introduction to Petroleum Refining

 Electrochemical Reactions
Cell Elements
Anode Cathode

External
Electrolyte
Circuit

Introduction to Petroleum Refining

 Electrochemical Reactions
• Overall Reaction
Zn + 2 H + + 2Cl - ® Zn 2+ + 2Cl - + H 2 ­
Zn + 2 H + ® Zn 2+ + H 2 ­

• Oxidation Reaction (Anodic Reaction)

Zn ® Zn 2+ + 2e -

• Reduction Reaction (Cathodic Reaction)

+ -
2 H + 2e ® H 2 ­

Introduction to Petroleum Refining

 Electrochemical Reactions

Introduction to Petroleum Refining

 Electrochemical Reactions
Anodic Process Cathodic Process

M ® M + n + ne -

Introduction to Petroleum Refining

 Electrochemical Reactions
Cathodic Process

• Oxygen Reduction (Acid Solutions)

O2 + 4 H + + 4e - ® 2 H 2O
• Oxygen Reduction (Neutral and Alkaline Solutions)
- -
O2 + 2 H 2O + 4e ® 4OH
• Hydrogen Evolution
+ -
2 H + 2e ® H 2 ­
• Metal Ion Reduction
Fe3+ + e - ® Fe 2+
• Metal Deposition 2+ -
Cu + 2e ® Cu
Introduction to Petroleum Refining
 Electrochemical Reactions
• Combined Anodic and Cathodic Processes

Introduction to Petroleum Refining

 Area Effects
• Current Density – current flow per unit
area Steel Rivet Copper Rivet
(Anode) (Cathode)

Copper Plate Steel Plate

(Cathode) (Anode)

Current Density in Cathode - low Current Density in Cathode - high

Cathodic Protection – slight Cathodic Protection – high
Corrosion - severe Corrosion – not noticeable

Catchment Area Principle

Introduction to Petroleum Refining
 CORROSION
CONTROL

Introduction to Petroleum Refining

 Corrosion Failure

failure of the function of the metal due to

corrosion within a period that is significantly less
than the anticipated life of the structure

Predictable Unpredictable

Introduction to Petroleum Refining

 Corrosion Failure
Predictable
• The knowledge and technology are available but have not
been utilized by the designer (i.e., wrong choice of
materials, introduction of crevices and bimetallic contacts)
• The knowledge and technology are available, but have not
been applied for economic reasons (i.e., inadequate
pretreatment of steel prior to painting and the use of
unprotected mild steel for silencers and exhaust system of
cars)

Introduction to Petroleum Refining

 Corrosion Failure
Unpredictable
• The design has been based on specific environmental
conditions which have subsequently changed during the
operation of the process (i.e., the catastrophic oxidation
and failure of steel bolts in nuclear reactors resulting from
an increase in the temperature of carbon dioxide)
• There is insufficient knowledge and experience of the
metal, alloy or the environment to predict with certainty
that failure will not occur (new alloys that have been
subjected to an extensive series of carefully planned
corrosion tests but have failed in service)

Introduction to Petroleum Refining

 Corrosion Control
• Selection of a particular metal or alloy in
preference to all others
• Rejection of metals in favor of a non-metallic
material (i.e., glass-reinforced polymer)
• Use of a less corrosion-resistant material and
reduction of the aggressiveness of the
environment (changing composition,
removing deleterious impurities, lowering
temperature, lowering velocity, adding
corrosion inhibitors)
Introduction to Petroleum Refining
 Methods of Corrosion Control
Contact with
Selection of
Design other
Materials
Materials

Mechanical
Coatings Environment
Factors

Corrosion Supervision
Interfacial
Testing and and
Potential
Monitoring Inspection

Introduction to Petroleum Refining

 Methods of Corrosion Control
• Selection of Materials

q Select metal or alloy (or non-metallic material)for the

particular environmental conditions (composition,
temperature, velocity, etc.)
q Take into account mechanical and physical properties,
availability, method of fabrication and overall cost of
structure

Introduction to Petroleum Refining

 Methods of Corrosion Control
• Design

q Make provision in the design for applying metallic or non-

metallic coatings or applying anodic or cathodic
protection

Introduction to Petroleum Refining

 Methods of Corrosion Control
• Design

q Avoid geometric configurations that facilitate corrosive

conditions, such as:
v features that trap dust, moisture and water
v crevices (or else fill them in) and situations where deposits can
form on the metal surface
v designs that lead to erosion-corrosion or to cavitation damage
v designs that result in inaccessible areas that cannot be re-
protected (i.e., by maintenance painting)
v designs that lead to heterogeneities in the metal (differences
in thermal treatment) or in the environment (differences in
temperature, velocity)
Introduction to Petroleum Refining
 Methods of Corrosion Control
• Contact with other Materials

q Avoid metal-metal or metal-non-metallic contacting

materials that facilitate corrosion such as:
v bimetallic couples in which a large area of a more positive
metal (ex: Cu) is in contact with a small area of a less noble
metal (Fe, Zn, Al)
v metals in contact with absorbent materials that maintain
constantly wet conditions or in the case of passive metals that
exclude oxygen
v contact (or enclosure in a confined space) with substances
that give off corrosive vapors (ex: certain woods and plastics)

Introduction to Petroleum Refining

 Methods of Corrosion Control
• Mechanical Factors

q Avoid stresses (magnitude and type)and environmental

conditions that lead to stress-corrosion, cracking,
corrosion fatigue or fretting corrosion
q Stress corrosion cracking: avoid the use of alloys that are
susceptible in the environment under consideration;
ensure that the external and internal stresses are kept to
a minimum
q Corrosion Fatigue: ensure that the metal is adequately
protected by a corrosion-resistant coating

Introduction to Petroleum Refining

 Methods of Corrosion Control
• Coatings

q Make provision in the design for applying an appropriate

protective coating such as:
v metal reaction products, i.e, anodic oxide films on Al,
phosphate coatings on steel (for subsequent painting or
impregnation with grease), chromate films on light metals and
alloys (Zn, Al, Cd, Mg)
v Metallic coatings that form protective barriers (Ni, Cr) and also
protect the substrate by sacrificial action (Zn,Al, Cd on steel)
v Inorganic coatings (enamels, glasses, ceramics)
v Organic coatings (paints, plastics, greases)

Introduction to Petroleum Refining

 Methods of Corrosion Control
• Environment

q Make environment less aggressive by removing

constituents that facilitate corrosion
q Decrease temperature and velocity
q Where possible, prevent access of water and moisture
q For atmospheric corrosion, dehumidify air, remove solid
particles, add volatile corrosion inhibitors (for steel)
q For aqueous corrosion, remove dissolved O2, increase pH
(for steel), add inhibitors

Introduction to Petroleum Refining

 Methods of Corrosion Control
• Interfacial Potential

q Make the interfacial potential sufficiently negative by

using sacrificial anodes or impressed current
q Make the interfacial potential sufficiently positive to
cause passivation (confined to metals that passivate in
the environment under consideration)

Introduction to Petroleum Refining

 Methods of Corrosion Control
• Corrosion Testing and Monitoring

q Corrosion Testing – done when there is no information on

the behavior of a metal or alloy or a fabrication under
specific environmental conditions
q Monitor composition of environment, corrosion rate of
metal, interfacial potential, etc. to ensure that control is
effective

Introduction to Petroleum Refining

 Methods of Corrosion Control
• Supervision and Inspection

q Ensure that the application of a corrosion control is

adequately supervised and inspected in accordance with
the specification or code of practice

Introduction to Petroleum Refining

Introduction to
Corrosion What is Corrosion?
Corrosion Chemistry
Corrosion Control
PRT 110
Introduction to Petroleum
Refining