CHAPTER 16 – CORROSION & DEGRADATION OF MATERIALS

16.1 INTRODUCTION
 Deteriorative mechanisms are different for the three material types
o Metals —> there is actual material loss either by dissolution (corrosion) or by the
formation of non-metallic scale or film (oxidation)
o Ceramics —> relatively resistant to deterioration (usually occurs at elevated temperature
or in extreme environments)
 Process typically also called corrosion
o Polymers —> termed degradation
 Mechanisms and consequences differ from metals & ceramics
 Polymers may dissolve when exposed to a liquid solvent, or they might absorb
the solvent and swell
 Electromagnetic radiation (primarily UV) and heat may cause alterations in their
mechanical structures
 Corrosion – the destructive and unintentional attack on a metal
o Electrochemical process
o Usually begins at the surface

16.2 ELECTROCHEMICAL CONSIDERATIONS

 For metallic materials, corrosion process is normally electrochemical —> chemical rxn in which
there is a transfer of electrons from one chemical species to another
 Metal atoms characteristically lose valence electrons – oxidation reaction
o M —> Mn+ + ne–
 The site at which oxidation takes place is called the anode
 The electrons generated from each metal atom that is oxidized must be transferred to and
become part of another chemical species – reduction reaction
o Some metals undergo corrosion in acid solutions which have a high concentration of H+
ions
 H+ ions are reduced as follows: 2H+ + 2e– —> H2(g)
o For an acid solution with dissolved oxygen, this reduction will occur:
 O2 + 2H2O + 4e– —> 4(OH–)
o Any metal ions present in solution may also be reduced
 Multivalent states: Mn+ + e– —> M(n-1)+
 Full reduction: Mn+ + ne– —> M
 The site at which reduction takes place is called the cathode
 It is possible for multiple reduction rxns to occur simultaneously**
 An overall electrochemical rxn must consist of at least one ox. and one red. rxn —> will be the
sum of these two
o Individual ox. and red. rxns are called half-reactions
 The total rate of ox. must equal the total rate of red. —> all electrons generated through ox.
must be consumed through red. (no net accumulation of electrical charge)
 As a consequence of oxidation, metal ions may either go into the corroding solution as ions or
form an insoluble compound with nonmetallic elements (ex. rust, Fe(OH)3)
Electrode Potentials
 Not all metallic materials ox. to form ions with the same degree of ease
 In Figure 16.2, two electrochemical cells are connected, allowing the movement of electrons
between cells, but are separated by a membrane that prevents the solutions from mixing
o Reduction will occur for copper at the expense of oxidation of iron
 Cu2+ + Fe —> Cu + Fe2+
o Cu2+ ions will deposit as metallic copper on the copper electrode – electrodeposit
o Iron dissolves (corrodes) on the other side of the cell and goes into solution as Fe2+ ions
o When a current passes through the external circuit, electrons generated from the ox. of
iron flow to the copper cell in order that Cu2+ be red.
o There is also some net ion motion from each cell to the other across the membrane
o This is called a galvanic couple – two metals electrically connected in a liquid electrolyte
in which one metal becomes an anode and corrodes while the other acts as a cathode
o An electric potential (voltage) exists between the two cell halves —> specific to the
nature of the metals in each cell (electrode pairs) and the temperature of rxn.
 Can be measured by a voltmeter connected in the external circuit
 Magnitude of this voltage can be thought of as the driving force for the
electrochemical redox rxn
 Standard half-cell – a pure metal electrode immersed in a 1 M solution of its ions at 25ºC

The Standard emf Series

 Wanted to establish a reference point (reference cell) to which other cell halves may be
compared
 Standard hydrogen reference half-cell —> arbitrarily chosen to be the reference cell
o Inert platinum electrode in 1 M solution of H+ ions saturated with hydrogen gas that is
bubbled through the solution at a pressure of 1 atm and a temp. of 25ºC
 o Platinum does not take part in the electrochem. rxn – only acts as a surface on which the
hydrogen atoms may be ox. or hydrogen ions may be red.
 Electromotive force (emf) series —> generated by coupling the standard hydrogen electrode
with standard half-cells of various metals and ranking them according to measured voltage

 Metals at the top are termed noble (chemically inert) —> gold and platinum
 As you move down the table, the metals become increasingly active – susceptible to
oxidation**
o Sodium and potassium have the highest reactivities
 Emf series table gives half-reactions as reduction rxns
o For oxidation rxns the direction of the rxn is reversed and the sign of the voltage is
switched**
 The potentials shown are known as the standard potential (V0) of the half-rxn
 The overall cell potential is: ∆V0 = V0red – V0ox
  For the rxn to occur spontaneously, ∆V0 must be positive
o If the cell potential is negative, the spontaneous cell direction is the reverse
 When standard half-cells are coupled together, the metal that lies lower on the emf series
table experiences oxidation and the the higher one is reduced**

Influence of Concentration and Temp. on Cell Potential

 Emf series applies only to ideal electrochemical cells —> pure metals in 1 M solutions of their
ions at 25ºC
 Altering temp. or solution concentration or using alloy electrodes instead of pure metals changes
the cell potential**
o In some cases, the spontaneous rxn direction may be reversed**
 Non-standard cells are governed by the Nernst equation

o R – gas constant (8.314 J/mol*K)

o n – number of electrons participating in either of the half-cell rxns
o F – Faraday’s constant (96,500 C/mol)
 Just like with standard potentials, ∆V must be positive for rxn spontaneity**

The Galvanic Series

 Emf series has limited utility since it only relates to idealized conditions
 A more realistic and practical ranking is provided by the Galvanic series
o Represents the relative reactivities of various metals and commercial alloys in seawater
 The alloys near the top are cathodic and unreactive; the alloys near the bottom are most anodic
 No voltages provided

 In both emf and Galvanic series, there is a high degree of correspondence between the relative
positions of the pure base metals
 Most metals and alloys are subject to ox. or corrosion to one degree or another in a wide variety
of environments
o They are more stable in an ionic state than as metals**
o There is a net decrease in free energy going from metallic to oxidized states
 Consequently, essentially all metals occur in nature as compounds (ex. oxides, hydroxides,
carbonates, silicates, sulfides, sulfates)
o Two notable exceptions: gold and platinum (the noble metals)**
 Oxidation of these metals in most environments is not favourable, therefore
they exist in their metallic state
16.3 CORROSION RATES
 Emf half-cell potentials are thermodynamic parameters that relate to systems at equilibrium
 Real corroding systems are not at equilibrium —> there is a flow of electrons from anode to
cathode**
o This means that the half-cell potential parameters cannot be applied
  The half-cell potentials represent the magnitude of a driving force (or the tendency for the
occurrence of the particular half-cell rxn) —> they provide info on direction of rxn sponteneity
but provide no info on corrosion rates**
o Magnitude of ∆V for a specific corrosion situation does not indicate anything about rate
of corrosion
 Corrosion penetration rate (CPR) – thickness loss of material per unit time

o W – weight loss after exposure time t

o ρ – density
o A – exposed specimen area

o K – constant (magnitude depends on system of units used)

o mpy = mils per year
o mm/yr = millimetres per year
 For most applications, CPR less than ~20mpy is acceptable**
 There is electric current associated with electrochem. corrosion rxns and we can express
corrosion rate in terms of this current
o We use current density (i), which is current per unit surface area of material corroding
o The rate, r, has units of [mol/m2*s]

 n – number of electrons associated with the ionization of each metal atom

 F = 96,500 C/mol

16.4 PREDICTION OF CORROSION RATES

 Remember that non-equilibrium systems will not have a potential matching the emf series
potential
 The displacement of each electrode potential from its equilibrium value is termed polarization
o The magnitude of this displacement is the overvoltage (η)
o Overvoltage is expressed in terms of +/- volts (or millivolts) relative to the equilibrium
potential
o η = measured potential – equilibrium potential
 Two types of polarization: activation and concentration

Activation Polarization
 Active polarization – the condition in which the rxn rate is controlled by the step in the series
that occurs at the slowest rate
o An activation energy barrier is associated with this slowest, rate-limiting step (hence the
name)
 Consider the reduction of hydrogen ions to form bubbles of hydrogen gas on the surface of a zinc
electrode…
o (1) Absorption of H+ ions from the solution onto the zinc surface
o (2) Electron transfer from the zinc to form a hydrogen atom
 H+ + e– —> H
o (3) Combining of two hydrogen atoms to form a molecule of hydrogen
 2H —> H2
o (4) The coalescence of many hydrogen molecule to form a bubble
 The slowest of these steps determines the rate of the overall rxn**
 For activation polarization the relationship between overvoltage and current density is:

o β and i0 are constants for the particular half-cell

o i0 is the exchange current density
 Determined experimentally and varies from system to system
 Equilibrium for some particular half-cell rxn is a dynamic state on the atomic level —> ox. and
red. processes are occurring, both at the same rate**
o There is no net rxn!
o Equilibrium exists when rred. = rox.
 Exchange current density (i0) is the current density at equilibrium

 Figure 16.7
o Line segment with slope of +β = oxidation half-rxn
 o Line segment with slope of –β = reduction half-rxn
o Both line segments originate at i0 (H2/H+) and at zero overvoltage —> the point where
the system is at equilibrium and there is no net rxn**

Concentration Polarization
 Concentration polarization – exists when the rxn rate is limited by diffusion in the solution
 Consider the hydrogen evolution red. rxn…
o When rxn rate is low and/or the concentration of H+ is high, there is always adequate
supply of hydrogen ions available in solution at the region near the electrode interface
o However, at high rates and/or low H+ concentrations, a depletion zone may form in the
viscinity of the interface —> H+ ions are not replenished at a rate sufficient to keep up
with the rxn**
o Diffusion of H+ to the interface is rate controlling and the system is said to be
concentration polarized
  Overvoltage is independent of current density until i approches iL —> at this point ηc decreases
abruptly in magnitude**
o iL – limiting diffusion current density
o R – gas constant
o T – absolute temperature (K)
o n – number of electrons associated with the ionization of each metal atom
o F – Faraday’s const.
 Both concentration and activation polarization are possible for reduction rxns
o The total overvoltage is the sum of both overvoltage contributions

Corrosion Rates from Polarization Data

 Two types of systems are discussed
o (1) Both ox. and red. rxns are rate limited by activation polarization
o (2) Both concentration and activation polarization control the red. rxn and only
activation polarization is important for ox. rxn
 Case (1):
o Consider the corrosion of zinc immersed in an acid solution…
o Red. of H+ ions to form H2 gas bubbles occurs at the surface of the zinc; zinc oxidizes
o No net charge accumulation may result from these two rxns —> rates of red. and ox. are
equal
 o Figure 16.10
 The potentials of the uncoupled hydrogen and zinc half-cells are indicated along
with their respective exchange current densities
 Straight line segments represent each half rxn (hydrogen red. and zinc ox.)
 Upon immersion, both hydrogen and zinc experience activation polarization
along their respective lines
 Recall that ox. and red. rates must be equal, which is possible only at the
intersection of the two line segments
 The intersection occurs at the corrosion potential, Vc, and the corrosion
current density, ic
 Case (2):
o Treated similarly
o Figure 16.11 shows both polarization curves
 Corrosion potential and corrosion current density correspond to the point at
which the ox. and red. lines intersect

16.5 PASSIVITY
 Passivity – under particular environmental conditions, some normally active metals and alloys
lose their chemical reactivity and become extremely inert
 Displayed by chromium, iron, nickel, titanium, and many other alloys
 Passive behaviour caused by formation of a highly adherent and very thin oxide film on the
metal surface, which serves as a protective barrier to further corrosion**
 Stainless steels are highly resistant to corrosion in a wide range of atmospheres due to
passivation**
o Contain at least 11% chromium —> minimizes formation of rust due to protective
surface film formation in oxidizing atmospheres
 Aluminum also passivates, thus is highly corrosion resistant
 If damaged, the protective film normally reforms very rapidly
 BUT, a change in the environment may cause a passivated material to revert to an active state**
o Ex. alter concentration of the active corrosive species
o Subsequent damage to a pre-existing passive film could result in a substantial increase in
corrosion rate —> as much as 100,000 times**
 Figure 16.12 – shows the shape of the polarization curve for a metal that passivates
o At relatively low values —> active region, linear behaviour
o With increasing potential, the current density suddenly decreases to a very low value
that remains independent of potential —> passive region
o At even higher potentials, the current density again increases with potential —>
transpassive region
 Metals can experience both active and passive behaviour, depending on the corrosion
environment (Figure 16.13)
o S-shaped oxidation polarization curve for an active-passive metal M
o Also shows reduction polarization lines for two different solutions (Line 1 and Line 2)
o The points of intersection indicating the corrosion current density of M in each solution
 Depending on whether the solution curve intersects in the active or passive
region, the corrosion rate will differ (proportional to the current density)
16.6 ENVIRONMENTAL EFFECTS
 Variables in a corrosion environment: fluid velocity, temperature, composition
o These variables can have an influence on the corrosion properties of the materials that
are in contact with it
 Increasing fluid velocity enhances the rate of corrosion due to erosive effects (in most cases)**
 The rates of most chemical rxns (including corrosion rxns) rise with increasing temp**
 Increasing the concentration of the corrosive species will produce more rapid rate of corrosion
(in most cases)**
o Ex. increase H+ ions in acids
o Note: for materials capable of passivation, raising the corrosive content may result in an
active-to-passive transition, which considerably lowers corrosion
 Cold working/plastically deforming ductile metals is used to increase their strength
o A cold-worked metal is more susceptible to corrosion than the same metal in an
annealed state**
o Differential cold working can cause the corrosion properties to differ within the same
specimen

16.7 FORMS OF CORROSION

 We classify corrosion according to the manner in which it is manifest
 Metallic corrosion classified into 8 forms:
o Uniform
o Galvanic
o Crevice
o Pitting
 o Intergranular
o Selective leaching
o Erosion-corrosion
o Stress corrosion
o (Also) Hydrogen embrittlement – a type of failure rather than a form of corrosion
 Often produced by hydrogen that is generated from corrosion rxns

Uniform Attack
 Occurs with equivalent intensity over the entire exposed surface and often leaves behind scale
or deposit
 Redox rxns occur randomly over the surface
 Ex. rusting of steel and iron, tarnishing of silverware
 Most common form of corrosion**
 Least objectionable form, because it can be predicted and designed for with relative ease**

Galvanic Corrosion
 Occurs when two metals or alloys having different compositions are electrically coupled while
exposed to an electrolyte
o Same type of corrosion discussed in section 16.2
 The less noble (more reactive) metal in the particular environment experiences corrosion; the
more inert metal (cathode) is protected from corrosion
 Depending on the nature of the solution, one or more of the reduction reactions occurs at the
surface of the cathode material
 Galvanic series —> discusses relative reactivities in seawater
o When two alloys are coupled in seawater, the one lower in the series experiences
corrosion
o Some alloys are grouped in brackets —> little danger of corrosion if alloys within a single
bracket are coupled
o Some alloys are listed twice, in both active and passive states
 Ex. Nickel, stainless steel
 The rate of galvanic attach depends on the relative anode-to-cathode surface areas that are
exposed to the electrolyte
o The rate is related directly to the cathode-anode area ratio**
o For a given cathode area, a smaller anode corrodes more rapidly than a larger one
 Corrosion rate depends on current density (current per unit area of corroding
surface)
 Anode area is small relative to that of the cathode = high current density
 Reducing the effects of galvanic corrosion:
o If coupling of dissimilar metals is necessary, choose two that are close together in the
galvanic series
o Avoid an unfavourable anode-to-cathode surface area ratio —> use anode area as large
as possible
o Electrically insulate dissimilar metals from each other
o Electrically connect a third, anodic material to the other two —> cathodic protection

Crevice Corrosion
  Occurs as a consequence of concentration differences of ions or dissolved gases in the
electrolyte solution between two regions of the same metal piece (concentration cell)
 For such a concentration cell, corrosion occurs in the locale that has the lower concentration**
 Ex. corrosion that occurs in crevices and recesses or under deposits of dirt or corrosion products
where the solution becomes stagnant and there is localized depletion of dissolved oxygen
 The crevice must be wide enough for the solution to penetrate yet narrow enough for
stagnancy**
o Usually, width is several thousandths of an inch
 Mechanism:
o After oxygen has been depleted within the crevice, oxidation of the metal occurs at this
position
o Electrons from the rxn are conducted through the metal to adjacent external regions,
where they are consumed by reduction
 In many aqueous environments, the solution within the crevice has been found to develop high
concentrations of H+ and Cl– ions
 Prevention:
o Using welded instead of riveted or bolted joints
o Using nonabsorbent gaskets when possible
o Removing accumulated deposits frequently
o Designing contaminant vessels to avoid stagnant areas and ensure complete drainage

Pitting
 Very localized corrosion attack in which small pits or holes form
 Usually penetrate from top of a horizontal surface downward in a nearly vertical direction
 Extremely insidious type of corrosion**
o Often goes undetected and with very little material loss until failure occurs
 Mechanism:
o Probably similar to crevice corrosion
o Oxidation occurs within the pit itself, with complementary reduction at the surface
o Supposed that gravity causes the pit to grow downward —> the solution at the pit tip
becoming more concentrated and dense as pit growth progresses
 o A pit may be initiated by a localized surface defect such as a scratch or slight variation in
composition
 Specimens with highly polished surfaces display greater resistance to pitting
corrosion**
 Stainless steels are somewhat susceptible to this form of corrosion
o Alloying with ~2% molybdenum enhances their resistance significantly

Intergranular Corrosion
 Occurs preferentially along grain boundaries (for some alloys and in specific environments)
 Net result is that a macroscopic specimen disintegrates along its grain boundaries
 Type of corrosion especially prevalent in some stainless steels**
o When heated between 500 and 800ºC for sufficiently long periods, these alloys become
sensitized to intergranular attack
o This heat treatment permits the formation of small precipitate particles of chromium
carbide (Cr23C6)

o These particles form along the grain boundaries —> both chromium and carbon must
diffuse to the grain boundaries to form the precipitates, which leaves a chromium-
depleted zone adjacent to the grain boundary
 This grain boundary is now highly susceptible to corrosion**
 Particularly severe problem in the welding of stainless steels —> weld decay
 Protection (of stainless steels):
o Subjecting the sensitized material to a high-temperature heat treatment in which all the
chromium carbide particles redissolve
o Lowering the carbon content below 0.03 wt% C so that carbide formation is minimal
o Alloying the stainless steel with another metal (I.e. niobium or titanium), which has a
greater tendency to form carbides than does chromium
 Forces Cr to stay in solid solution

Selective Leaching
 Found in solid solution alloys
  Occurs when one element or constituent is preferentially removed as a consequence of
corrosion processes
 Most common example: dezincification of brass
o Zinc is selectively leached from a copper-zinc brass alloy
o The material changes from yellow to a red or copper colour
 Mechanical properties of the alloy are significantly impaired —> only a porous mass of copper
remains in the region that has been dezincified
 Selective leaching may also occur with other alloy systems
o Aluminum, iron, cobalt, chromium, and other elements are vulnerable to preferential
removal**

Erosion-Corrosion
 Arises from the combined action of chemical attack and mechanical abrasion or wear as a
consequence of fluid motion
 Virtually all metal alloys are susceptible to erosion-corrosion (to some degree)
 It is especially harmful to alloys that passivate by forming a protective surface film**
o The abrasive action may erode away the film, leaving exposed a bare metal surface
o If the coating is not capable of continuously and rapidly re-forming as a protective
barrier, corrosion may be severe
 Relatively soft metals are also sensitive to this form of attack**
o Ex. copper, lead
 Can usually be identified by surface grooves and waves having contours that are characteristic of
the flow of fluid
 The nature of the fluid can have dramatic influence on the corrosion behaviour
o Increasing fluid velocity normally enhances the rate of corrosion
o A solution is more erosive when bubbles and suspended particulate solids are present**
 Erosion-corrosion is commonly found in piping (esp. at bends, elbows, and abrupt changes in
pipe diameter)**
o These are positions where the fluid changes directions or flow suddenly becomes
turbulent
 Propellers, turbine blades, valves, and pumps are also susceptible
 Prevention:
o Change the design to eliminate fluid turbulence and impingement effects (best way**)
o Other materials used that are inherently resistant to erosion
o Removal of particulates and bubbles from the solution

Stress Corrosion
 Also called stress corrosion cracking
 Results from the combined action of an applied tensile stress and a corrosive environment —>
both influences are necessary**
 Some materials that are virtually inert in a particular corrosive medium becomes susceptible to
this form of corrosion when a stress is applied
 Small cracks form and then propagate in a direction perpendicular to the stress
o Result is that failure may eventually occur
o Failure behaviour is characteristic of that for a brittle material, even though the metal
alloy is intrinsically ductile
  Most alloys are susceptible to stress corrosion in specific environments, esp. at moderate stress
levels
o Ex. most stainless steels stress corrode in solutions containing chloride ions
o Ex. brasses are esp. susceptible when exposed to ammonia
 The stress that produces stress cracking does not need to be externally applied**
o It may be a residual stress that results from rapid temperature changes and uneven
contraction or occur for two-phase alloys in which each phase has a different coefficient
of expansion
o Gaseous and solid corrosion products that are entrapped internally can give rise to
internal stresses
 Prevention:
o Lower the magnitude of the stress (best method**)
 Can be done by reducing the external load or increasing the cross-sectional area
perpendicular to the applied stress
o An appropriate heat treatment may be used to anneal out any residual thermal stresses

Hydrogen Embrittlement
 Various metal alloys (specifically some steels) experience a significant reduction in ductility and
tensile strength when atomic hydrogen (H) penetrates into the material —> hydrogen
embrittlement
 Also called hydrogen induced cracking and hydrogen stress cracking
 Technically hydrogen embrittlement is a type of failure —> in response to applied or residual
tensile stresses, brittle fracture occurs catastrophically as cracks grow and rapidly propagate
 Hydrogen in atomic form (H, as opposed to molecular form, H2) diffuses interstitially through the
crystal lattice**
 Concentrations as low as several parts per million can lead to cracking
 Hydrogen-induced cracks are most often transgranular**
 Mechanism likely to do with interference of dislocation motion by the dissolved hydrogen
 Hydrogen embrittlement is similar to stress corrosion —> normally ductile materials experience
brittle fracture when exposed to both tensile stress and a corrosive atmosphere
o Distinguishing between the two —> interaction w/ applied electric currents
 Cathodic protection reduces or causes a cessation of stress corrosion**
 Cathodic protection may lead to the initiation or enhancement of hydrogen
embrittlement**
 For H.E. to occur, some source of hydrogen must be present & the possibility of formation of its
atomic species
o Example situations:
 Pickling of steels in sulfuric acid
 Electroplating
 The presence of hydrogen-bearing atmospheres (including water vapour) at
elevated temperatures
 During welding & heat treatments
 The presence of poisons (ex. sulfur & arsenic compounds) accelerates H.E.**
o These substances retard the formation of molecular hydrogen thus increasing the time
atomic hydrogen exists at metal surfaces
o Hydrogen sulfide – most aggressive poison
 Found in petroleum fluids, natural gas, oil-well brines, geothermal fluids
  High strength steels are susceptible to H.E. —> increasing strength tends to enhance a material’s
susceptibility
 FCC alloys are relatively resistant to H.E. (likely because they are inherently highly ductile)
o Strain hardening these alloys makes them susceptible
 Prevention:
o Reducing tensile strength of the alloy via heat treatment
o Removing the source of hydrogen
o “Baking” the alloy at an elevated temp. to drive out any dissolved hydrogen
o Substituting a more H.E.-resistant alloy

16.8 CORROSION ENVIRONMENTS

 Corrosion environments include: the atmosphere, aqueous solutions, soils, acids, bases,
inorganic solvents, molten salts, liquid metals, the human body
o Atmospheric corrosion accounts for the greatest losses**
 Moisture containing dissolved oxygen is the primary corrosive agent**
o Other substances may contribute (ex. sulfur compounds, NaCl)
 Especially true of marine atmospheres —> highly corrosive b/c of the presence of NaCl
 Metals commonly used for atmospheric applications include:
o Alloys of aluminum & copper
o Galvanized steel
 Water environments
o Freshwater – normally contains dissolved oxygen as well as minerals (several of which
account for hardness)
 Cast iron, steel, aluminum, copper, brass, and some stainless steels are generally
suitable for freshwater use
o Seawater – contains ~3.5% salt (predominantly NaCl) and some minerals and organic
matter
 Generally more corrosive than freshwater**
 Frequently produces pitting and crevice corrosion**
 Titanium, brass, some bronzes, copper-nickel alloys, and Ni-Cr-Mo alloys are
highly corrosion resistant in seawater
 Soils have a range of compositions and susceptibilities to corrosion
o Compositional variables: moisture, oxygen, salt content, alkalinity, acidity, presence of
certain bacteria
o Cast iron & plain carbon steels are economical for underground structures

16.9 CORROSION PREVENTION

 This section discusses general techniques for corrosion prevention (see Section 16.7 for type-
specific prevention)
 The most common and easiest method is through proper selection of materials for the given
corrosive environment
o Cost may be a significant factor
 Changing the character of the environment, if possible
o Lowering fluid temperature and/or velocity usually reduces corrosion rate
o Increasing/decreasing the concentration of certain species in the solution will have a
positive effect
  Inhibitors – substances that, when added in relatively low concentrations to the environment,
decrease its corrosiveness
o Many possible mechanisms:
 Some react w/ and virtually eliminate a chemically active species in the solution
(ex. dissolved oxygen)
 Other molecules attach themselves to the corroding surface and interfere with
either the red. or ox. or form a very thin protective coating
o Normally used in closed systems such as automobile radiators, steam boilers
 Because dissolved oxygen may enhance the corrosivity of many solutions, design considerations
should be made to include provision for exclusion of air
 Physical barriers to corrosion are applied on surfaces in the form of films and coatings
o Essential that the coating must be virtually nonreactive in the corrosive environment**
o All three material types (metals, ceramics, polymers) are used as coatings for metals

Cathodic Protection
 One of the most effective means of corrosion protection**
o In some situations, it can completely stop corrosion
 Can be used for all eight types of corrosion**

 Involves supplying, from an external source, electrons to the metal to be protected —> makes it
a cathode
o The reaction that would otherwise take place (oxidation of metal) is forced in the
reverse direction (reduction)
 One cathodic protection technique employs a galvanic couple – the metal to be protected is
electrically connected to another metal that is more reactive in the particular environment
o This metal experiences oxidation and, upon giving up electrons, protects the first metal
from corrosion —> sacrificial anode
o Magnesium and zinc are commonly used (since they are highly anodic)**
 Galvanizing – a layer of zinc is applied to the surface of steel by hot dipping
o In the atmosphere and most aqueous environments, zinc is anodic and will cathodically
protect the steel if there is any surface damage
o Any corrosion to the zinc will occur very slowly because the ratio of anode-to-cathode
surface area is very large**
 Another method: source of electrons is an impressed current from an external DC power source
o The negative terminal of the power source is connected to the structure to be protected
 o The other terminal is joined to an inert anode (often graphite)
 In Figure 16.23(b) this anode is buried in soil – high conductivity backfill material
provides good electrical contact between the anode and the surrounding soil
o A current path exists between the cathode and anode through the intervening soil –
completes the electrical circuit
 Cathodic protection is especially useful in preventing corrosion of water heaters, underground
tanks and pipes, and marine equipment