MODULE 2

CORROSION OF METALS AND ALLOYS

CHE 431
Dr. Samuel SANNI
Department of Chemical Engineering
INTRODUCTION: FORMS OF CORROSION (REVIEW)
• Corrosion as an electrochemical or mechanical process
• The different forms of corrosion include:
• Galvanic: the corrosion caused by the difference in electrode potentials of
metals in the presence of an electrolyte e.g. corrosion of carbon/mild steel
in acids
• Fretting: Corrosion of metal alloys caused by friction i.e. the sliding of one
metal over another e.g. the wearing of the disc plate of car engines caused
by the iron rod running through the orifice in the disc.
• Gas corrosion:
- Carbon dioxide corrosion: This type results from the diffusion of the gas
onto and through a metal in the presence of an electrolyte; very common in
the petroleum industries (petroleum processing in columns/pipes carrying
Liquified Petroleum Gas -LPG)
DEFINITION OF TERMS
• Corrosion: Gradual deterioration of a metal caused by induced wear
as in the case of mechanical corrosion or the presence of an
electrolyte electrochemical corrosion
• Corrosion inhibition: prevention or control of corrosion
• Corrosion inhibitors: materials/methods employed to control
corrosion
• Corrossivity: Extent of corrosion
• Electrolyte: Potential environment or medium/environment where
corrosion exists or could take place
• Electrochemical cell: a system set up by the difference in electrode
potentials in metals when in contact with an electrolyte; anode is
positive, cathode is negative
• Electrolytic cell: a system set up by difference in electrode potential of
metals where the anode is the negative electrode while the cathode is
positive
• Resistivity: a measure of resistance offered with respect to corrosion
• Electrode: One of the terminals of the electrochemical or electrolytic
cell
• Anodic half reactions: reactions occurring at the anode terminal of
the electrochemical cell
• Cathodic half reactions: reactions occurring at the cathode terminal
of the electrochemical cell
- Oxygen corrosion: this results from the diffusion & penetration of oxygen
molecule through metals/metal alloys in the presence of an electrolyte
(oxidation of metals.

- Hydrogen sulphide corrosion: As the name implies, is caused by the

diffusion and penetration of the gas through a metal in the presence of an
electrolyte (petroleum processing caused by sulphur in crude)
• Microbial corrosion: This type is caused by the presence of microbes
e.g. Mycobacterium in a favourable environment (electrolyte).
• Erosion corrosion: This is caused by the leaching of a surface which is
entrenched by the removal of a passive layer that may have been a
barrier to corrosion. The corrosion of submerged pipes in soils caused
by the difference in soil pH.
• Stress Corrosion: This results from the concentration of stress over a
metal surface; compression of metals when beating them into sheets
• Crevice corrosion: this type occurs due to the accumulation of a
processed material/fluid in narrow paths of metal conduits
• Fatigue corrosion: this is caused by the continuous cyclic loading of a
metal surface. E.g. the rolling of steel drums up the metal covers of
the backside of pickup trucks.
• Leaching: the partial eviction of one composite in an alloy thus
enriching the other
• Stray/direct current corrosion: this is informed by the transference of
current through a metal e.g. railway tracks such that the metal
surface becomes deformed by the appearance of corrosion spots
• Corrosion testing: These are the methods used to ascertain the extent
or type of corrosion. The methods for testing for the occurrence of
corrosion & the performance of inhibitors include:
- Static test
- Wheel test
- Bubble test
- The u-glass tube
- Rotating cylinder electrode
- The rotating cage
- Impingment method
- The rotating flow loop
• The static test:
- This is an initial test conducted when the metal is in an immobile
phase i.e. the electrolyte is static

- The method uses the electrochemical method of measuring corrosion

- The temperature of the system must not exceed 80 oC.

- It does not require high skills during operation & has good
reproducibility
• Wheel test:
- Metals are placed in a solution of brine as inhibitors where there is
low flow of the corrosive fluid & hydrocarbon saturated with
measurable hydrogen sulphide and carbon dioxide concentrations

- The method uses the weight loss method of measuring corrosion

- The temperature must be less than 80 Oc

- There is low level of reproducibility of data generated for repeated

experiments

- Materials are expensive and test duration is 24 h

• Bubble test:
- A glass apparatus containing several tubes

- Carbon dioxide is bubbled in as the causative

- The tubes are in cells connected to a automated measuring probe

which bypasses the liquid phase when measuring the corrosion rate

- The limitation of this test is that it barely mimics field measurements

of actual corrosion rate
• U-Glass tube:

- Flow is stimulated in U-shaped glass tube with two chambers using a stirrer

- In the chambers are the metal samples attached to thermometers

- Carbon dioxide is bubbled into the tube at not more than 1 m/s with a wall
shear stress of 5.5 kPa

- Weight loss method is used to determine corrosion rates.

- The results can be regenerated.

• Rotating cylinder electrode

- Similar in design to the rotating disc electrode but has a cylinder side surface rather than a flat end

- Turbulent flows within speeds of 1000 rpm can be generated

- The equipment is easy to use, has low cost

- The results are reproducible

- Currently the best method for corrosion/inhibitor testing

- Period for tests should not exceed 6 h which may not be appropriate to ascertain the performance of an
inhibitor/effect of corrosion over longer periods

- Adopts corrosion rate measurements from potentiostats/polarization curves for corrosion rate measurement.
• The rotating cage test:

- This equipment has a plastic holder for holding samples

- Has a motor that causes turbulence at a speed of 160 rpm which transfers its turbulence to
the fluid through perforations in the plate

- When taking measurements, the plastic holders containing the samples are dipped into a
sealed cell that houses the corroding agent/fluid

- It uses the weight loss method for taking corrosion rates.

- Cannot be used in situations of high turbulent flows.

• Impingment test:

- Adopts the combined methods of corrosion monitoring/survey and inhibitor testing

- The equipment used consists of a central cell with 4 extensions having spray
nozzles

- An impeller is installed in the cell

- The method uses the weight loss method for taking corrosion rates and has
good reproducibility but involves complex instrumentation and lab scale of
the equipment is not available (is only manufactured on industrial scale)
(i) Re-circulating flow facility

- It consists of two vessels

- Here, the test fluids are treated before carrying out the test

- The operating pressure is about 4 atm

- Equipment houses a centrifugal pump and heating device

- Same fluid is recirculated and the absence of effect on fluid on test results can only be
guaranteed in 24 h

- Good reproducibility

- Equipment is not manufactured on commercial scale

MEASUREMENT OF CORROSION
- Weight loss method: this is judged by the difference in the weight of the
metal before and after corrosion
- Potentiodynamic measurement test: this is an equipment which measures
the difference in electrode potential and the variation of current on a
metal surface after it’s been subjected to corrosion
- Linear resistance: this works on the principle of polarization of light; a
direct current is applied to the surface of the metal and measurements are
then taken from a

• Assignment: Discuss the various methods of measuring corrosion, the

mechanism behind the corrosion type identified, the equipment used and
the operating principle of the equipment.
MATERIALS SELECTION
• Material selection is the process of identifying choice metals/alloys
that are suitable for specific application i.e. corrosion resistant metals
- Type/nature of operation
- Type of metal: Resistance of the metal
- The fluid: the fluid to be transported or collected
- The environment: whether affected by the environment or not
CORROSION MODELS
• This refers to tools for predicting internal pitting corrosion
(i) De Waard-Milliams Models: Corrosion rates are measured in the lab
using X-52 carbon steel specimens 0.1 % concentrated NaCl solution,
saturated with C02 and oxygen-free nitrogen. Then corrosion rate
measurements are taken via linear polarization technique.
(ii) Srinivasan Model: This takes its bearing from the de Waard-Milliams
relationship of CO2 and corrosion rate with the inclusion of some
additional correction factors.
Steps:
- Determination of system pH.
- The dissolved C02 (or H2S) that contributes to pH is determined in terms of
the partial pressure of the acid gas, bicarbonates and temperature. Note: In
addition to pH reduction, the Srinivasan Model takes into account the
inherent roles of hydrogen sulphide gas
(iii) Crolet Model: This model predicts potential/probability of the
occurrence of corrosion in oil wells. Data is based on C02 corrosion
from different oil fields.
Complementary situations for pitting corrosion:
- The presence of water and its contact with metal
- The sufficiency of the water in quantity to aid corrosion since low
water cut reservoir-tubing/well-lines experience very minimal or low
corrosion rates water must have a sufficient i.e. the potential for
corrosion is determined by water volume
- Favourable conditions for corrosion to develop locally, i.e. an active
anode should remain poised near protected or slowly corroding areas
(iv) Nesic Models: Are models developed from the reactions occuring on a metal
surface in an electrochemical cell i.e. a water-C02 system.

The various interactions in the transport processes of species in the system,

including H ions, CO2, H2C03, and Fe2+ are all taken into cognizance; there are two
versions of the model:

Version 1: Glass-cell experiments of electrochemical reactions of CO2 bubbled

through acid solution.
Version 2: This has to do with the tendency for the formation of corrosion scales
i.e., the ratio of rate of precipitation of corrosion products and the rate of
deterioration/degradation of the metal prior the formation of a film on the metal
surface.
Two scaling cases identified in the Nesic model:
1. lower precipitation rate with respect to corrosion rate (expressed in the same
units); this results in the formation of a porous unprotective
2. Higher precipitation rate with respect to corrosion rate which then results in the
formation of a dense protective iron carbonate film.
(v) The Mishra Model
A corrosion-rate equation developed on the basis of fundamental
reaction rate principle. Here, experimental measurements were
validated using model predictions. The model, determines the effects
of steel microstructures and velocity of flow of the corrosive medium
on rate of corrosion rate.
Model’s short-coming:
The model application is limited by when the corrosion is controlled by
diffusion of e.g. especially after the formation of a poised/stable
corrosion product/scale on the surface of the metal.
(vi) Anderko Model: Has its origin in a thermodynamic model which
specifies the aqueous system and an electrochemical model (i.e. oxidation
and reduction reactions of iron and hydrogen, water, carbonic acid and
hydrogen sulphide) which help to estimate the rate of corrosion of carbon
steels in the presence of CO2, H2S, and brine.

The model also accounts for the formation of iron carbonate and sulphide
scales and the effect of temperature and type of electrolyte on the general
corrosion rate of the metal.

(vii) The Oddo Model

In this model, iron carbonate formation/deposition is accounted using the
de Waard and Milliams model; however, there is an introduction of another
scale correction factor which helps to account for the effects of the presence
of calcium carbonate on metallic corrosion; suitable for velocity applications
less than 3 m/s.
(ix) The SSH Model
A worst-case scenario model which suffices for lab measurements <
100°C and for combined lab and field measurements at temperatures
>100°C.

(x) The Adam Model: Has its origin in the determination of the
operating constraints e.g. temperature of condensate wells

(xi) Nyborg Model: An integration of the 1993 and 1995 versions of the
de Waard Milliams models with an existing three-phase flow model.
The temperature, pressure and liquid flow velocity profiles derived
from the model are used to make numerical estimates of the partial
pressure of carbon dioxide, solution pH and corrosion rates along a
pipeline.
(vii) Dayalan Model: Is a mechanistic/computational model that is
programmed to predict the corrosion rates of carbon steel caused by
the flowing of CO2-burdened petroleum pipelines in the oil and gas
industry.
It also includes, the reaction kinetics, mechanism, mass transfer of
species, electrochemical and chemical equilibrium reactions

(viii) Pots/Limiting corrosion rate model: A mechanistic model whose

rate-determining steps for the prediction of the effects of CO2
corrosion rate and fluid on a metal are assumed to be largely controlled
by transport and production of protons and carbonic acid at the
diffusion and reaction boundaries.
CORROSION PREVENTION/INHIBITION
• Corrosion prevention is the avoidance of corrosion or control of
corrosion in progress
- Preventive measures include:
(i) Cathodic protection: Impressed current or sacrificial anode:
- impressed current: this is the application of current in a reverse
direction to the point where corrosion exists
- sacrificial anode: this is the coating of a metal with a metal higher up
in the electrochemical series such that the coating metal ends up
being sacrificed for the coated/protected metal
(ii) lubrication: this is the application of lubricant to a metal surface to
prevent wear e.g. the oiling of bicycle bearings to prevent wear/friction
(iii) Painting & Coating: The application of layers of pigments which
provide some colouring for the metal surface. Often times these paints
are liquid/gas-proofs which avoid the penetration of water, other
liquids and gaseous substances

(iv) Inspection & monitoring: To date, this remains the most efficient
means of identifying and controlling corrosion because it entails
carrying out routine/periodic checks in order to ascertain the status of
a metal surface.

(v) Chemical Dosing: this has to do with the injection of chemicals e.g.
glutaraldehyde, sodium thiosulphate etc known as inhibitors which
provide some form of protection for the metals.
PROJECTS: REFERENCE ARTICLES FROM TOP RATED PUBLICATIONS IN THE
SUBJECT AREA
• Top publications would be downloaded and students would be required to
reproduce the works, identify gaps and learn how to initiate research
• CORROSION TESTS: Students would be distributed into groups with leaders for
some practical assignments where they shall purchase metals fabricated in
Mechanical Engineering Department of CU in order to carry out corrosion
tests
- The students will dip the metals in different corrosion media that mimic some
form of corrosion in a typical industry
- Results would be collated over a period of time
- Corrosion measurement methods already identified will then be applied
- The use of weight loss & potentiodynamic tests to measure corrosion,
calculation of corrosion rates, weight reduction etc.
- Group presentations
 CORROSION MECHANISMS
• Mechanisms of corrosion refer to the underlying principles/theories
that explain how the different types of corrosion take place
• Equations for reactions:
- The writing and balancing of equations which indicate the
transference of electrons from the anode to the cathode of an
electrochemical cell.
Note:
The severity of corrosion is informed by the cathode to anode ratio I.e.
a high cathode to anode ratio informs high rate of corrosion while the
reverse relates to lesser corrosion.
The unit of corrosion rate: Corrosion rate is measured in length/year
i.e. mm/year or mass/area.time (flux)
 Some corrosion reactions and their
equilibrium constants
• Dissolution of carbondioxide CO2(g) CO2 Ksol ¼C CO2=PCO2
• Water dissociation H2O H (ion) + O (ion) Kwa = CH (SUb) + CoH (sub)
• Carbondioxide hydration CO2 +H2O H2CO3 Khy CH2CO3/CCO2
• Assignment: write out the corrosion reactions for the reactions listed
below and their equilibrium constants:
(i) Carbonic acid dissociation
(ii) Bicarbonate anion dissociation
(iii) Acetic acid dissociation
(iv) Hydrogen sulphate anion dissociation
 CORROSION IN THE INDUSTRY
• Several forms of corrosion take place in the industry:
- Chemical industry: the causative is acid or the presence of other
forms of chemicals e.g. sulphur, that aid corrosion
- Automobile industry: several forms of corrosion that exist in the
automobile industry include:
(I) Fretting corrosion: crank shaft
(II) Galvanic corrosion: engine parts
(III) Carbon dioxide corrosion: corrosion of car exhausts caused by the
release of carbon monoxide which is further oxidized to carbon
dioxide which stimulates corrosion
- Corrosion in the Petroleum industry
Several types that are common in the petroleum industry include:
(i) Oxygen corrosion: caused by the oxidation of pipes, columns, heat exchangers,
reactors, furnaces, pumps, compressors, drums, separators internals or their
external surfaces by the presence of oxygen which results in the appearance of
pits.
(ii) Sweet corrosion/carbon dioxide corrosion: Caused by the dissolution of carbon
dioxide in an electrolyte in aqueous acetate which produces the acid that aids
corrosion
(iii) Sour / hydrogen sulphide corrosion: Caused by the dissolution of the gas in an
aqueous medium/electrolyte which forms sulphuric acid or the reduction of
the gas to sulphur which aids corrosion
(iv) Microbial corrosion: Caused by the association of microbial colonies whose
resulting effect is identified by a black slime/deposit on the metal surface
(v) Crevice corrosion: Corrosion that exists as a result of the presence of an
immobile phase/liquid in the narrow clearance of metallic pipes/conduits.
- Chemical Industry
Chemical manufacturers: The production of corrosive chemicals
Production of HCl, sulphuric acid, carbonic acid, ethanoic acid, gluconic
acid, sulphur etc

Combustion reactions: this leads to the release/formation of carbon

dioxide and water which aid corrosion
 ELECTROCHEMISTRY OF CORROSION
• Iron /steel:
Fe Fe2+ + 2e- (1) (anodic reaction) electron loss
4 possible cathodic reactions (electron gain):
O2 + 4H + 4e- 2H2O (2) oxygen reduction in acid solution
½ O2 + H2O + 2e- 2OH- (3) oxygen reduction in neutral/basic solution
2H+ + 2e- H2 (4) hydrogen evolution from acidic solution
2H2O + 2e- H2 + 2OH- evolution of hydrogen from neutral water
Corrosion mechanism for sweet corrosion
• Equation for sweet corrosion reaction:
• H2CO3 + e- H + HCO3- (1)
• 2H H2 (2)
• With steel reacting, the reaction is given as
• Fe Fe2+ + 2e- (3)
• Overall reaction:
• CO2 + H2O + Fe FeCO3 + H2 (4)

Assignment: identify a type of corrosion and write out the corrosion

mechanisms
• CO2 corrosion:
Fe + CO2 + H2O FeCO3 + H2 (5) or the formation of Fe3O4 @ higher temps
(protective or unprotective scales depending on prevailing conditions)
Anodic reaction:
Fe Fe2+ + 2e- (6) Anodic dissolution of iron in acid soln (the
reaction is PH dependent) with reaction order wrt OH- between 1 & 2 for PH < 4; otherwise
it ranges between 0 & 1.
Cathodic reactions:
2H+ + 2e- H2 (7)
2H2CO3 + 2e- H2 + 2HCO3- (8); at PH > 5, and low partial press of CO2,
hydrogen evolution from water becomes important. At higher PH, there’s possible
reduction of the bicarbonate iron
2HCO3- + 2e- H2 + 2(CO3)2-
2H2O + 2e- H2 + 2OH- (9)
• H2S corrosion:
Fe + H2S + H2O FeS + 2H +H2O (10)
NOTE: Mechanism for formation of scales
Fe2+ (CO3)2- FeCO3 (11)
When the solubility of a salt is exceeded, it begins to precipitate out of
solution thus clinging to the metal surface (protective/unprotective
scales may result).
Inward diffusion of causative and outward diffusion of target metal
Acetic acid (effect is highly pronounced @ higher temp & lower PH):
2CH3COOH + 2e- H2 + 2CH3COO- (12)
Fe2+ + 2CH3COO- Fe(CH3COO)2 (13)
FACTORS AFFECTING CORROSION
• PH of environment (acidic/basic)
• Concentration of ionic species
• Nature of electrolyte/metal
• Amount of dissolved gases/salts
• Partial pressures (for gas corrosion)
• Temperature of the system
• Flow
• Condensation
• Addition of corrosion inhibitors
 Current Technologies for Combatting Corrosion

• The use of lasers/laser beams/additive protection

• The use of nanomaterials such as carbon nanotubes

• The use of benign materials/oils extracted from plant sources

• The combination of chemicals for enhanced protection

 CONCLUSIONS
• Corrosion is not only a surface phenomena; it also affects the internal
walls & other parts of equipment
• Corrosion can be controlled
• Corrosion is not limited to electrochemical reactions i.e. it is clear that
mechanical wearing/grinding is also a type of corrosion
• Corrosion can only be controlled when the mechanism for its
occurrence is known
• Continuous monitoring and inspection still remains the most
appropriate way of controlling/avoiding corrosion
 Thank you all
for being part of my
corrosion splendour