MMT4253

MARINE CORROSION
(KAKISAN MARIN)

Dr. Mohammad Fakhratul Ridwan bin Zulkifli

Maritime Technology Programme
Faculty of Ocean Engineering Technology
Universiti Malaysia Terengganu
fakhratulz@umt.edu.my
Topic 5 Corrosion Monitoring and Prevention
5.1 Introduction
5.2 Corrosion Monitoring
5.3 Corrosion Prevention Methods
5.1 Introduction
• Within the sphere of corrosion control and prevention, there are technical
options such as cathodic and anodic protection, materials selection, chemical
dosing and the application of internal and external coatings.
• The field of corrosion measurement, control, and prevention covers a very
broad spectrum of technical activities.
• Corrosion measurement employs a variety of techniques to determine how
corrosive the environment is and at what rate metal loss is being experienced.
• Corrosion measurement is the quantitative method by which the effectiveness
of corrosion control and prevention techniques can be evaluated and provides
the feedback to enable corrosion control and prevention methods to be
optimized.
• A wide variety of corrosion measurement techniques exists, including:

Fluid
Non Destructive Operational Data Electrochemistry
Testing • pH • Potential
• Ultrasonic testing • Flow rate measurement
• Radiography • Potentiostatic
(velocity)
• Thermograph • Pressure measurement
• Eddy • Temperature • Potentiodynamic
current/magnetic measurement
flux • A.C. impedance

Analytical Corrosion Monitoring

Chemistry • Weight loss coupons
• pH measurement • Electrical resistance
• Dissolved gas (O2, • Linear polarization
CO2, H2S) • Hydrogen
• Metal ion count penetration
(Fe2+, Fe3+) • Galvanic current
• Microbiological
analysis
5.2 Corrosion Monitoring
• Corrosion monitoring techniques can help in several ways
• By providing an early warning that damaging process conditions exist which
may result in a corrosion- induced failure.
• By studying the correlation of changes in process parameters and their effect
on system corrosivity.
• By diagnosing a particular corrosion problem, identifying its cause and the
rate controlling parameters, such as pressure, temperature, pH, flow rate, etc.
• By evaluating the effectiveness of a corrosion control/prevention technique
such as chemical inhibition and the determination of optimal applications.
• By providing management information relating to the maintenance
requirements and ongoing condition of plant.
 5.2 Corrosion Monitoring

These corrosion monitoring techniques have been successfully applied and are used
Corrosion Monitoring in an increasing range of applications because:
 Weight loss coupons  The techniques are easy to understand and implement.
 Electrical resistance  Equipment reliability has been demonstrated in the field environment over
 Linear polarization many years of operational application.
 Hydrogen  Results are easy to interpret.
penetration  Measuring equipment can be made intrinsically safe for hazardous area
 Galvanic current operation.
 Users have experienced significant economic benefit through reduced plant
down time and plant life extension.
5.2.1 Weight loss coupons
• The Weight Loss technique is a simple corrosion monitoring method
involving exposing a specimen to a process environment, then
analyzing it for weight loss to determine corrosion rate.
• This versatile method forms the baseline for many corrosion
monitoring programs and allows for studying various corrosion
phenomena such as:
• Stress-assisted corrosion
• Bimetallic (galvanic) attack
• Differential aeration
• Heat-affected zones
5.2.1 Weight loss coupons
• Advantages of weight loss coupons are that:
• The technique is applicable to all environments - gases, liquids, solids/particulate flow.
• Visual inspection can be undertaken.
• Corrosion deposits can be observed and analyzed.
• Weight loss can be readily determined and corrosion rate easily calculated.
• Localized corrosion can be identified and measured.
• Inhibitor performance can be easily assessed.
• In a typical monitoring program, coupons are exposed for a 90-day duration
before being removed for a laboratory analysis.
• This gives basic corrosion rate measurements at a frequency of four times per
year.
• The coupon technique's limitation are:
• Inability to pinpoint the timing of a corrosion upset and
• May not detect significant weight loss if the upset peak value and duration are not
substantial.
5.2.2 Electrical Resistance (ER) Monitoring
• ER probes provide a basic measurement of metal loss, but unlike
coupons, the value of metal loss can be measured at any time, as
frequently as required, while the probe is in-situ and permanently
exposed to the process stream.
• The technique is applicable to all environments - gases, liquids,
solids/particulate flow.
5.2.2 Electrical Resistance (ER) Monitoring
• The ER technique measures the change in Ohmic resistance
of a corroding metal element exposed to the process stream.
• The action of corrosion on the surface of the element
produces a decrease in its cross-sectional area with a
corresponding increase in its electrical resistance.
• The increase in resistance can be related directly to metal
loss and the metal loss as a function of time is by definition
the corrosion rate.
• The response time for ER monitoring is far shorter than that
for weight loss coupons.
• The technique is applicable to all environments - gases,
liquids, solids/particulate flow.
• The graph shows typical response times.
• ER probes have all the advantages of coupons, plus:
• Direct corrosion rates can be obtained.
• Probe remains installed in-line until operational life has been
exhausted.
• They respond quickly to corrosion upsets and can be used to
trigger an alarm.
5.2.3 Linear Polarization Resistance (LPR) Monitoring
• The LPR technique simplifies complex electrochemical theory for
industrial corrosion measurement.
• It involves applying a voltage to an electrode in a solution to measure
corrosion rate instantly.
• LPR is effective in clean aqueous environments but not in gases or
water/oil emulsions due to electrode fouling.
5.2.4 Galvanic Monitoring
• The galvanic monitoring technique, also known as Zero Resistance
Ammetry (ZRA) is another electrochemical measuring technique.
• Two electrodes of dissimilar metals are exposed to the process fluid.
When immersed in solution, a natural voltage (potential) difference
exits between the electrodes.
• The current generated due to this potential difference relates to the
rate of corrosion which is occurring on the more active of the Application of zero resistance ammeter to
electrode couple. real time measurement of redox control in
• Galvanic monitoring is applicable to the following electrode molten chloride salts
couples:
• Bimetallic corrosion
• Crevice and pitting attack
• Corrosion assisted cracking
• Corrosion by highly oxidizing species
• Weld decay
• Galvanic current measurement has found its widest applications in
water injection systems where dissolved oxygen concentrations are a Experimental setup for Zero Resistance
primary concern. Oxygen leaking into such systems greatly Ammetry (ZRA) study
increases galvanic currents and thus the corrosion rate of steel
process components.
• Galvanic monitoring systems are used to provide an indication that
oxygen may be invading injection waters through leaking gaskets or
5.2.5 Hydrogen Penetration Monitoring
• In acidic process environments, hydrogen
is a by-product of the corrosion reaction.
• Hydrogen generated in such a reaction can
be absorbed by steel particularly when
traces of sulphide or cyanide are present.
• This may lead to hydrogen induced failure
by one or more of several mechanisms.
• The concept of hydrogen probes is to
detect the amount of hydrogen permeating
through the steel by mechanical or
electrochemical measurement and to use
this as a qualitative indication of corrosion
rate.
Evaluation of Hydrogen Permeation into High-Strength Steel
during Corrosion in Different Marine Corrosion Zones
5.2.6 Application of Corrosion Monitoring

Corrosion monitoring may be used in any industry such as:

5.3 Corrosion Prevention Methods
5.3.1 Coatings
• A coating can be defined as a fluid that forms a solid, continuous,
adherent film or barrier by some physical or chemical means when
applied to a surface. This film is designed to enhance, beautify, or
protect the surface to which it has been applied.
• Consists of six basic components:
• Binders,
• Pigments,
• Extenders or fillers,
• Solvents,
• Rheology modifiers, and
• Special additives.
5.3.1.1 Types of Coatings
5.3.1.2 Three Types of Anti-corrosion Coatings
5.3.1.3 Applying coating
5.3.1.4 Binder
• Binders are the polymer components that form the continuous film.
• They hold all other components together, adhere to the substrate, and provide the
paint with its basic generic type.
• Binders may be classified by their method of film formation:
• Thermoplastic or
• Thermosetting
• Those that function by simply drying (solvent evaporation) are thermoplastic.
Vinyls and chlorinated rubbers are examples of thermoplastic binders. They are
generally softened by heat and re-dissolved by the appropriate solvents.
• In the case of thermosetting polymers, the binder is chemically changed by either
an atmospheric component, such as water (moisture cure urethanes) or oxygen
(alkyds), or with another type of chemical usually in the form of a co-reactant
(two-component epoxies and urethanes). The reaction can also take place upon
baking (baked enamels) or with ultraviolet or electron beam radiation.
 • The major types of binders are:
• Acrylics – weather resistance
• Alkyds – generally for mild environment
• Epoxies – heavy-duty corrosion resistance
• Phenolics – immersion in alkalies or mild acids
• Polyesters – strong acids
• Silicates – used in zinc-rich coatings
• Silicones – for high temperatures
• Urethanes – flexibility and UV resistance
• Vinyls – corrosion resistance

https://www.corrosionalliance.com/coat/coating-composition-
and-properties/
5.3.1.5 Pigments
• Pigments in coatings provide color and opacity. There are two types:
inorganic and organic. Pigment selection is crucial for properties like
pH stability, UV resistance, and chemical resistance to prevent coating
degradation. Proper selection protects the binder and ensures film
stability.
5.3.1.6 Extenders
• Extenders are inert solids used in paints to enhance properties like
hardness, resistance, and gloss without affecting color. Materials like
mica, aluminum flakes, and fibers provide specific benefits such as
protection, light reflection, and strength. Common types include clay,
talc, and silica.
5.3.1.7 Solvents
• Solvents are used to adjust coating viscosity by dissolving or diluting
binders. The solvent choice must match the resin to ensure proper
evaporation rate without performance issues.
• Multiple solvents are often combined to achieve the desired balance.
Solvents affect flash point and VOC compliance in coatings due to
environmental regulations.
• The types of solvents are classified by their molecular structure:
• Aliphatic and aromatic hydrocarbons
• Alcohols
• Esters
• Ethers
• Ketones
5.3.1.8 Rheological Modifiers
• Raw materials impact liquid coating flow. Rheology studies how
coatings respond to shear during application, pumping, and mixing.
• Coatings must stay fluid for spraying but not settle, run, or sag.
Rheological modifiers include fumed silicas, treated clays,
polyamides, thickeners, cellulosics, and castor oil derivatives. Solvent
choice affects these modifiers and requires a balanced formulation.
5.3.1.9 Additives
• There are several types of miscellaneous coating additives to provide
for a variety of special needs and conditions.
• There are waxes, surfactants, wetting aids, fungicides, ultraviolet light
absorbers, antioxidants, catalysts, and anti-mar agents to name a few.
5.3.2 Inhibitors
Chemical substance that when present in the corrosion system at a suitable concentration decreases the
corrosion rate, without significantly changing the concentration of any corrosive agent
• Corrosion inhibitors may be classified as cathodic, anodic, or mixed, depending on
whether their influence is mainly in retarding the cathodic or anodic reaction of the
corrosion process or both of them.
• As a result, they cause a shift of the corrosion potential of the inhibited metal toward
respectively either the cathodic or the anodic directions or they substantially leave the
metal corrosion potential more or less unchanged.
• The inhibition of anodic or cathodic corrosion reactions can be due to the reduction of
the active surface area of a metal and/or to a change of the activation energy of the
oxidation or reduction process in corrosion.
• The combination of cathodic and anodic corrosion inhibitors often determines
improved protection and allows to reduce the inhibitor concentration.
• Whichever the reaction hindered by the corrosion inhibitor, it will interact at the
metal/solution interface by forming a film, which may be of three different types:
• passivating film;
• precipitation film, and
• adsorption film.
5.3.2.1 Passivating film
• Passivating oxide films are 30–200 Å thick and afford excellent
corrosion protection.
• Among them, classical oxidizing inhibitors can be found, such as
chromates and nitrites, now largely abandoned because of toxicity
concerns, except in cases where corrosion can pose severe human
safety concerns (e.g., in aeronautical industry and building
construction).
• This class includes also non-oxidizing inhibitors, such as tungstates
and molybdates, affording their passivating effect only in aerated
solutions.
• 5.3.2.1 Precipitation film
• Precipitation film-type inhibitors are chemicals forming insoluble
protective films by reaction with soluble species in the environments
(e.g., phosphonates and polyphosphates, forming protective films with
calcium ions in solution) or with the protected metal ions (e.g., copper-
benzotriazole (BTA) salt film).
• These films may be porous and not perfectly adherent, in this case
resulting in fairly good corrosion protection.
5.3.2.1 Adsorption film
• Inhibitors forming adsorption protective films are mainly organic
substances.
• They often have the molecular structure of a surfactant, with a
hydrophilic group capable to bond with the metal surface and a
hydrophobic part of the molecule protruding toward the solution bulk.
• Adsorbed inhibitor molecules limit oxygen diffusion and the water
access to the metal surface, so reducing the corrosion rate.
5.3.3 Sacrificial Anodes
• Sacrificial anodes consist of expendable electrodes, usually zinc,
aluminum or magnesium, or their alloys, whose natural potentials
provide adequate protective current to a structure.
• Impressed current systems are those that employ a direct current (DC)
power source to provide the necessary current.
5.3.3.1 Sacrificial Anode
• When iron and copper are attached in a galvanic cell, we have seen
that the result is the corrosion of the iron, with electrons flowing out of
the iron (the anode) and into the copper (the cathode).
• Suppose that we now place a zinc bar in the cell as illustrated below:
• Because of the potentials involved, the
electrons flow out of the zinc and into both
the iron and copper. protection of a ship's
hull in the vicinity of

• Thus the zinc corrodes and the iron and protection of an ordinary hot-
the bronze propeller
by zinc anodes

copper, which now both function as water heater with a

magnesium anode
cathodes, do not.
• This is the basis for sacrificial anode
protection, namely, the use of an
expendable anode to protect another metal
from corrosion.
5.3.3.2 Impressed Current Cathodic Protection (ICCP)
• In impressed current cathodic protection systems:
• Current can be supplied from sources like batteries, rectifiers, or generators.
• Anodes can be expendable steel or permanent materials like platinum. Steel
anodes need periodic replacement due to destruction.
• Permanent anodes like platinum are slowly destroyed or not destroyed.
• Steel structures in seawater are protected by polarizing to -0.85 volts against
reference electrodes.
• Selecting the right power supply voltage can
protect iron and copper from corrosion by making
them act as cathodes.
• The voltage should match the open-circuit
potential of the local anode to prevent current flow.
• A polarization diagram using a standard half-cell
can help determine the open circuit potential and
applied current.
• Adjust the power supply until the iron's potential
matches the open circuit potential of the local
anode.
• This method is used in impressed current
protection to prevent corrosion.
LIMITATION OF CATHODIC PROTECTION
• Maintenance: Cathodic protection systems require regular maintenance, such as checking and replacing the
anodes.
• Limited protection: Cathodic protection may not be effective in all environments, such as when there are
high levels of electrical interference or when the ship’s hull is in contact with non-conductive materials.
• Limited protection against mechanical damage: Cathodic protection doesn’t provide protection against
mechanical damage, it only protects the ship’s hull from corrosion
• Limited protection in areas with high salinity or other extreme conditions: Cathodic protection may not be
effective in areas with high salinity or other extreme conditions, and the anodes may need to be replaced
more frequently.

MARINE INDUSTRY APPLICATIONS FOR CATHODIC PROTECTION

• Ships
• offshore floaters
• subsea equipment
• harbours
• pipelines
• tanks
5.3.4 Anodic Protection
• Anodic protection is cost-effective and effective in
sulfuric acid, extending equipment life and reducing
corrosion.
• It reduces hydrogen permeation and embrittlement in
hard alloys. The system uses impressed current to
protect steel storage vessels through constant potential
application based on design parameters and
experimental measurements.
• Anodic protection systems use continuous proportional
controls to maintain optimal protective potential
between the storage tank and the reference electrode.
• Standard reference electrodes include calomel
electrodes. The system ensures uniform potential
distribution on the structure by flowing current between
the tank and a chromium-nickel steel cathode.
• Cathode materials like chromium-nickel steel and
Hastelloy C are used to minimize hydrogen evolution
and permeation.
The following are the requirements for designing anodic protection systems:
• The polarization potential should be determined from the potentiodynamic polarization curve. The variation of
the protective potential with time must be determined accurately.
• Avoid polarizing the system at a high rate through the passivation potential Epass, because of a drastic increase
of the critical current density, Icrit, at a high polarization rate.
• The cathode should be inert in the corrosive solution and electrochemically stable.
• The cathode materials must have low hydrogen overvoltage and small surface area to minimize hydrogen
permeation and embrittlement.
• The solution resistivity should be very low. The overall system resistivity should be controlled by the cathode
surface area.
• The system should be designed to avoid surface irregularities in the structure that may create a nonuniform
current distribution.
• The active-passive metal or alloy should have a low critical passivation current density
• Limitation of anodic protection.
• only applicable to active-passive metals
• installation cost is high
• Applications for anodic protection.
• Alkaline process equipment
• acid cooler for sulphuric acid storage
• Stainless steel heat exchanger for sulphuric acid storage