Corrosion and Protection of Metals

Chapter 1
The Technology and
Evolution of Corrosion
By
Dr. Al-Montaser Bellah Al-Ajlony

Summer-2018/2019

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 1.1 Introduction
Corrosion intrudes itself into many parts of our lives

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 1.2 Costs of Corrosion
• The Actual cost of corrosion on the economic
sectors can be classified as a direct and
indirect cost
• The direct cost of corrosion includes the actual
losses of parts or components due to their
corrosion.
• Annually the US economy loses tens of
billions due to direct corrosion losses.

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Direct cost of corrosion

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Direct cost of corrosion

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 The Indirect cost of corrosion
• The indirect cost resulting from actual or possible corrosion are
difficult to evaluate.
• Some of the more important sources of indirect cost are summarized
as follows
1- plants downtime: loss of production wile the plant is inoperable
during repairs. Example, the cost to replace power from a shutdown
nuclear power plant can run into millions dollars per day.
2- Loss of products: leaking containers, tanks and pipelines result in
significant losses products, which have a high cost. These leaks and
spills have a corresponding hazardous effect on the surrounding
environment and safety of the populace.
3- Loss of Efficiency: Accumulated corrosion products on heat
exchanger tubing and pipelines decrease the efficiency of heat
transfer and reduce the pumping capacity,respectively.

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 The Indirect cost of corrosion
4- Contamination: Soluble corrosion products can spoil chemical preparations
of soap, dyes, and pharmaceuticals, among others. A major problem in
many nuclear power generating plants is the transport of radioactive
corrosion products from the reactor core followed by deposition in other
parts of the cooling water system, necessitating dangerous and expensive
shutdowns to decontaminate.
5- Overdesign: In the absence of adequate corrosion rate information,
overdesign is required to ensure reasonable service life, resulting in wasted
resources, and greater power requirements for moving parts. Engineers
sometimes overdesign through ignorance of available information. The
needed information may not be available, however. Geologic storage of
high-level nuclear waste in deep repositories, mandated by the U.S.
Congress, requires containers that will maintain their integrity for 300 to
1000 years,

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 1.3 Definition
• Corrosion: is the destructive
result of chemical reaction
between metal or metal alloy
and its environment

• Metal atoms in nature are

present in a chemical
compounds (minerals [oxides,
sulfides, etc.])

• The same amount of energy

needed to extract metals from
their minerals are emitted
during the chemical reaction
that produce corrosion.

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 Other materials degradation
• Many nonmetallic materials, such as ceramics, consist of
metals that have their chemical reactivity satisfied by the
formation of bonds with other reactive ions, such as oxides
and silicates. Thus, such materials are chemically
unreactive, and they degrade by physical breakdown at high
temperature or by mechanical wear or erosion.

• Similarly, organic polymers (plastics) are relatively

unreactive because they have very stable covalent bonding,
primarily between carbon atoms.

• The degradation of such materials is not defined here as

corrosion.

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Corrosion Science and Engineering
• Corrosion science is the study of the chemical and metallurgical
processes that occur during corrosion. However, scientists are
sometimes devoted to the pursuit of pure knowledge, with little or
no perspective on the possible applications of their work.

• Corrosion engineering is the design and application of methods to

prevent corrosion. engineers often apply time-honored methods with
little or no understanding of the principles behind them.

• Ideally, science should be married to engineering so as to invent new

and better methods of prevention and apply existing methods more
intelligently and effectively. And that is the main goal of this course.

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1.4 Electrochemical Nature of Aqueous
Corrosion
• Nearly all metallic corrosion processes involve transfer of
electronic charge in aqueous solutions.

• Thus, it is necessary to discuss the electrochemical nature of

corrosion briefly, before continuing with descriptions of the
various forms of corrosion in the next sections

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 Electrochemical Reactions
• Consider an example of corrosion between zinc and hydrochloric acid
represented by the following overall reaction:

Zn + 2HCl ZnCl2 + H2 (1)

• Zinc reacts with the acid solution forming soluble zinc chloride and
liberating hydrogen bubbles on the surface.
• Reactions such as this are used, for surface cleaning and pickling of many
metals and alloys.
• In ionic form the reaction is

Zn + 2H+ + 2Cl-  Zn2+ + 2Cl- + H2 (2)

• Eliminating Cl- from both sides of the reaction gives

Zn + 2H+  Zn2+ + H2 (2)

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 Electrochemical Reactions
• Reaction (2) can be separated as follows:

Zn  Zn+2 + 2e- Anodic reaction. (3)

2H+ + 2e-  H2 Cathodic reaction. (4)

• Reaction (3), defined as the Anodic reaction, is an

oxidation in which zinc valence increases from 0 to +2,
“liberating electrons”
• while (4), defined as the Cathodic reaction, is a
reduction in which the oxidation state of hydrogen
decreases from +1 to 0, “consuming electrons”.

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 Electrochemical Reactions
• The composite reaction
involving charge transfer or
exchange of electrons is
shown schematically in this
Figure
• The metal dissolves by (3)
liberating electrons into the
bulk of the metal which
migrate to the adjoining
surface, where they react with
H+ in solution to form H2 by
(4).
• The summation of (3) and (4),
of course, gives (2)
• Water is required as the carrier
for ions, such as Zn2+ and H+,
and is called the electrolyte.

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 Anodic (Oxidation) Reactions
• All aqueous corrosion reactions are considered to be electrochemical.
• Most corrosion reactions do involve water in either the liquid or condensed
vapor phases.
• Even some "dry" corrosion reactions without water involve charge transfer
in a solid state electrolyte, and are considered still to be electrochemical.
• For corroding metals, the anodic reaction invariably is of ,the form

M  Mn+ + ne- (5)

• Examples in addition to (3) are

Fe  Fe2+ + 2e-
Ni  Ni2+ + 2e-
Al  Al3++3e-

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 Cathodic (Reduction) Reaction
• Cathodic reduction reactions significant to corrosion are few in number.
• The simplest and one of the most common is reduction of hydrogen ions
(2) in acid solution.
• Another is reduction of an oxidized ion in solution by a so-called redox
reaction; the
• most important example is reduction of ferric to ferrous ions,
Fe3++ e-  Fe2+.
Others, such as
Sn4++2e-  Sn2+
• The reduction of dissolved oxygen is often observed in neutral and acid
solutions exposed to ambient air.
• The respective reduction reactions are
O2+2H2O +4e- 4OH-
O2+4H++4e-  2H2O
• In the absence of all other reduction reactions, water will be reduced by
2H2O +2e- H2 + 2OH-
• which is equivalent to (4), assuming dissociation of water to H+ and OH-
and subtracting OH- from both sides of the reaction.

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 Polarization
• Electrochemical reactions such as (3) and (4) proceed only at finite rates.
• If electrons are made available to (4), the potential at the surface becomes
more negative, suggesting that excess electrons with their negative charges
accumulate at the metal/solution interface waiting for reaction.
• That is, the reaction is not fast enough to accommodate all the available
electrons.
• This negative potential change is called cathodic polarization.
• Similarly, a deficiency of electrons in the metal liberated by (3) at the
interface produces a positive potential change called anodic polarization.
• As the deficiency (polarization) becomes greater, the tendency for anodic
dissolution becomes greater.
• Anodic polarization thus represents a driving force for corrosion by the
anodic reaction (3), When surface potential measures more positive
(Section 2.3), the oxidizing (or corrosive) power of the solution increases
because the anodic polarization is greater.

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 Polarization
• In an aqueous electrolyte solution the surface will reach a steady state
potential, Ecorr which depends on the ability and rate at which electrons can
be exchanged by the available cathodic and anodic reactions.

• As the surface potential increases above Ecorr to E, the anodic reaction rate
or corrosion rate generally increases, as shown schematically in Figure 1.2.
• Anodic polanzation is defined
as εa= E - Ecorr.

• Without polarization, the

slightest driving force would
produce very high rates, and
the line in Figure 1.2 would be
horizontal with zero slope.

• Reaction rates and polarization

of electrochemical reactions at
metal surfaces are discussed in
more detail in Chapter 3.
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 Passivity
• In many metals, including
iron, nickel, chromium,
titanium, and cobalt, the
corrosion rate decreases
above some critical
potential Ep, as shown in
Figure 1.3.
• This corrosion resistance
above Ep despite a high
driving force for corrosion
(i.e., high anodic
polanzation), is defined as
passivity.
• Below Ep the alloy
corrodes at a relatively high
rate.

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 Passivity
• Passive corrosion rates are very low; a reduction of 103 to 106
times below the corrosion rate in the active state is not
unusual.
• Passivity is caused by formation of a thin, protective,
hydrated oxide, corrosion-product surface film that acts as a
barrier to the anodic dissolution reaction.
• Depending on the potential, or oxidizing power of the
solution, an alloy may exist in the passive state above Ep or in
the active state below it.
• For example, type 304 stainless steel is passive in aerated but
active in deaerated salt water,
• Fortunately, the list of active-passive metals includes many
used in our most common constructional alloys, which
consequently rely on passivity for corrosion resistance.

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 Passivity
• Chromium is a key alloying element forming resistant passive oxide
films on the surface.

• Although it cannot be used alone because of brittleness, chromium

enhances passivity when alloyed with other metals, especially iron
and nickel in the stainless steels.

• Passivity comes not without attendant problems.

• Because the passive film is thin and often fragile, its breakdown can
result in unpredictable localized forms of corrosion, including
pitting, corrosion in crevices, and embrittlement by stress corrosion
cracking.

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1.5 Forms of Corrosion
• Various forms of corrosion will be presented in this section as follows:

 Uniform Corrosion
 Galvanic Corrosion
 Crevice Corrosion
 Pitting Corrosion
 Erosion Corrosion
 Intergranular Corrosion
 Dealloying
 Environmentally Induced Cracking
 Hydrogen Damage

• Uniform corrosion accounts for the greatest tonnage of metal consumed.

• Yet the other localized forms, of corrosion are more insidious and difficult to
predict and control.
• While localized corrosion may not consume as much material, penetration and
failure are often more rapid.
• Hydrogen damage, more a metallurgical result of, than a form of corrosion is
included because of its importance and frequency.
• Each form of corrosion ,is described briefly in the next few slides.
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1.6 Corrosion Rate Determination
• Methods of exposure testing for corrosion measurement are,
fundamental in corrosion engineering and introduced in this section.
• The emphasis is on measurement of uniform corrosion rates by
weight loss of coupon specimens.
• However, exposure methods to determine localized attack are
essentially the same, differing only in the form of the specimen and
method of evaluation.
• It is necessary here to give only general descriptions of exposure
procedures, which are detailed in appropriately referenced ASTM
standards.
• Electrochemical methods are mentioned only in context with
exposure tests and again are discussed more fully in subsequent
chapters.

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 Objectives of corrosion testing
• Corrosion testing can have one or more of the following objectives.

o Screen available materials (alloys) to determine the best for a specific

application.
o Determine probable service life of equipment or a product.
o Evaluate new commercial alloys or processes.
o Assist in the evaluation and development of new corrosion resistant
alloys.
o Verify that an alloy lot (shipment) meets quality control specifications
before either acceptance or release.
o Evaluate environmental controls and variations (e.g, inhibitors).
o Determine the most economical means for reducing corrosion.
o Study corrosion mechanisms.

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Specimen preparation for exposure test
• Specimen coupons are fabricated from sheet or plate stock, which is
available for most common constructional alloys.
• Coupons are usually rectangular but may be round.
• The cheapest methods of fabrication are by punching, stamping, or
shearing, which create cold-worked edges.
• Since cold work often has a significant-effect on corrosion rate, the edges
need to be ground or machined to remove an amount at least equal to the
coupon thickness.
• Each coupon must be legibly, permanently, and uniquely identified,
preferably by stamping.
• However, uncontrolled residual stresses are produced which may be
undesirable in environments that cause environmentally induced cracking.
• Surface finish of the alloy as placed in service should be reproduced in test
coupons whenever possible.
• Surface abrasion with carbide or diamond papers to 120 grit is common
and can be produced without specialized equipment, although blasting with
sand, steel shot, or glass beads may be less expensive

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 Specimen Exposure – In-Lab
• In the laboratory a container must be selected for the
corrosive environment and the racks to hold the
coupons.
• The figure to the right shows a typical laboratory
reactor with facilities to control temperature, aeration
and reflux of vapor to prevent loss of solution by
evaporation or boiling.
• A rack is shown to hang the specimens immersed,
partially immersed, and in the vapor above the
solution.
• Corrosion is often maximized at the liquid line or in
the vapor.
• A minimum ratio of 100 to 200 liters per square
meter of exposed surface area is usually
recommended to avoid depletion of corrosive
ingredients in solution.
• The vessel would be an autoclave when temperatures
and pressures above the atmospheric boiling point
are required to simulate conditions in, for example,
pressurized boilers and nuclear steam generators.
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 Specimen Exposure – In-plant
• The process piping or vessels serve as the container plant exposures.
• Specimen racks for plant exposures are shown in Figure below
• The racks must be fabricated of materials that are resistant to the process
flow.
• Holder, shown in this figure can be mounted on a flange behind a gate
valve to overcomes the need to interrupt plant flow to install or remove
coupons
• It may also be convenient to install coupons in a bypass loop which can
be isolated from the main flow during installation and removal of coupons

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 Specimen Exposure – Atmosphere
• The figure below shows racks to hold panel specimens during atmospheric
exposures
• Specialized laboratory equipment is sometimes used to simulate or accelerate
environmental conditions in order to shorten the long exposure times required
by atmosphere-simulated service testing
• Uniform corrosion rates are normally calculated from coupon weight loss
• Microscopic, visual, and metallographic examinations are usually needed
instead of or in addition to weight-loss- determinations for localized forms of
corrosion

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Corrosion Rate Units and Calculations
• The corrosion rate in mils (1 mil=0.001-in.) penetration per year (MPY)
may be calculatbd from

• where W is weight loss in milligrams, D is density in grams per cubic

centimeter, A is area in square inches, and T is time in hours.
• Equation (6) can be derived readily by dimensional analysis.
• Other units fot W, D, A, and T simply change the value of the constant 534,
as discussed later in this section.
• Units of penetration per unit time are most desirable from an engineering
standpoint, but weight loss per unit area per unit time, often milligrams per
square decimeter per day (mdd), are sometimes used in research.
• For conversion, 1 MPY = 1.44 (mdd)/specific gravity

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 Corrosion rate conversion
• Conversions to equivalent metric penetration rates are:
• 1 mpy = 0.0254 mm/yr
• 1 mpy = 25.4 μm/yr
• 1 mpy = 2.9 nm/h
• 1 mpy = 0.805 pm/s,

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 Corrosion rate in metric units
• The proportionality constant, 534, in equattn (6) varies depending
on the units required for corrosion rate and used for the parameters
in the equation.

• where W,D, and T have the same units as for equation (6) but area,
A, is measured in square centimeters.

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 Planned Interval Tests
• Changes in the solution-corrosivity and alloy corrodibility
(corrosion rate) with time can be determined with a planned interval
testing program.
• From a set of four weight-loss coupons, numbered 1 to 4, the first
three are placed simultaneously in the same corrosive environment.
• Duplicate or more sets may be included as well for statistical
validity.

 Number 1 is removed after exposure of "unit" time, which might be

typically one day in a program of several days total duration, or
longer for lower corrosion rates.
 Number 2 is removed after exposure of time r.
 Number 3 is removed after exposure of time t + l.
 Number 4 replaces number 2 after the initial interval t and is
removed along with number 3 at time t + 1, giving an exposure time
of unity for number 4.

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 Planned Interval Tests
• A1 is the corrosion (weight loss or calculated corrosion rate) obtained from
number 1.
• At is the corrosion obtained from number 2.
• At + l is the corrosion obtained from number 3.
• A2 is the difference in conosion between nurnbers 2 and 3,
• B is the corrosion obtained from number 4.
• When B =A1 the corrosiveness of the environment is unchanged during the
time interval t.
• When B < A1, corrosiveness has decreased, and when B >A1 it has increased.
• When A2 = B the alloy corrodibility is unchanged.
• When A2 < B the corrodibility has decreased, and when A2> B it has
increased.
• Any combination of environment corrosivity and alloy corrodibility is
possible and can be obtained from planned interval testing.
• Repeating the procedure with varying r will yield more detailed effects of
time.

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 Electrical Resistance Probes
• The electrical resistance of any conductor is given by R=ρL/A, where ρ is the
resistivity, L is the length, and A is the cross-sectional area of the conductor.
• As corrosion reduces A, the resultant increase in R of a wire sensing element can be
used to monitor corrosion rate.
• Uniform loss of cross-section is measured by resistance increase instead of weight
loss.
• Corrosion rate over a given interval can be calculated from the slope of resistance
versus time.
• A commercial resistance probe design is shown in the figure below
• A temperature sensor is usually included to compensate for resistance variations
due to temperature changes.

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 Electrical Resistance Probes
• Resistance probe results can be obtained from liquid, vapor,
or mixed environments.
• The probes are small, easily installed, and can be wired into
computerized control stations which give a running
calculation of corrosion rate and remaining wall thickness.
• Alternatively, probe resistance can be measured manually
with conventional portable bridge instruments.
• High conductivity environments such as liquid metals or
molten salts allow parallel currents along the length of the
sensing element and preclude use of resistance probes.
• Conductive deposits (e.g., magnetite) accumulating on the
probe element during exposure have the same effect.
• Only uniform corrosion is measurable; pitting or otherwise
localized corrosion does not have the necessary proportionate
effect on cross-sectional area and probe resistance.
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End of Chapter-1

Thank you

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