LECTURE 14

CORROSION AND

WEAR
BSEE 4-3

CLIFFORD R. ESTRADA
CYRUS ANDREY D. PELAYO
SACHIE SOPHIA SAM T. PASCUA
TOPIC OUTLINE
01 CHEMICAL AND ELECTROMECHANICAL CORROSION

02 ELECTRODE POTENTIAL IN ELECTROCHEMICAL CELLS

03 CORROSION CURRENT AND POLARIZATION

04 TYPES OF AND PROTECTION AGAINST ELECTROCHEMICAL CORROSION

05 MICROBIAL DEGRADATION AND BIODEGRADABLE POLYMERS

06 OXIDATION AND OTHER GAS REACTIONS

07 WEAR AND EROSION

 CHEMICAL
AND
ELECTROMECHANICAL
CORROSION
CHEMICAL CORROSION
Is a process where a material dissolves
due to its reaction with the corrosive
liquid medium. This process continues
until either the material is consumed or
the corrosive liquid is fully saturated.
LIQUID METAL ATTACK
attack a solid at high-energy location such
as its grain boundaries. If continued to be
attacked, cracks will eventually appear and
grow.
SELECTIVE LEACHING
One element in an alloy selectively
dissolved or leached from the solid
material.
DISSOLUTION AND OXIDATION OF
CERAMICS
Ceramic refractories used to contain
molten metal during melting or refining
may be dissolved or degraded by the
slags produced on the metal surface.
CHEMICAL ATTACK ON POLYMERS
Aggressive solvents diffuse into low
molecular weight thermoplastic polymers
causing the polymer’s chain to swell
weakening the strength of the bonds.
 ELECTRODE POTENTIAL
IN
ELECTROCHEMICAL CELLS
ELECTROCHEMICAL CORROSION
Is the most common corrosion on metals.
it occurs when a metal atoms lose
electrons and becomes ions. Occurs most
frequently in aqueous medium.
ELECTROCHEMICAL CELL
An electric circuit that is formed in the
process of electrochemical corrosion.
 COMPONENTS OF
ELECTROCHEMICAL CELLS
ANODE CATHODE LIQUID ELECTROLYTE
Gives up Receives electrons A component that is
electrons to from the circuit by both in contact with
the circuit anode and cathode. Must
means of chemical, or
be conductive to
and corrodes cathode reaction.
complete the circuit.
ELECTROPLATING
Occurs when metal ions are transferred
from Anode onto the Cathode.
 ELECTROCHEMICAL
REACTIONS
Anode undergoes oxidation reaction by which
metal atoms are ionized. The metal ions enter
the electrolyte solution while the electrons
ANODE REACTION
leave the anode through the electrical
connection. Anode corrodes, or oxidizes due
to metal ions leaving the metal.

Is the reverse of anode reaction which the

metal ions either intentionally added to the
electrolyte or formed by the anode reaction, CATHODE REACTION IN
combine with electrons at the cathode. The ELECTROPLATING
anode’s metal ions plates out and covers the
cathode surface.
 ELECTROCHEMICAL
REACTIONS

When plating of a metal does not occur

CATHODE REACTION IN during the electrochemical corrosion. The
CORROSION reaction forms a gas, solid or liquid by
product at the cathode.
 ELECTROCHEMICAL
REACTIONS
GAS BYPRODUCT
In oxygen free liquid’s such as hydrochloric
acid (HCI), hydrogen gas may evolved at the
cathode.

If Zinc is added in the environment, the

reaction would be:
 ELECTROCHEMICAL
REACTIONS
SOLID BYPRODUCT In aerated water, oxygen is available to the
cathode, and hydroxy (OH)-, ions forms:

The oxygen electrode then enriches the

electrolyte in (OH)- ions. These ions reacts
with the positively charge metallic ions
producing a solid product such as rusting:
 ELECTROCHEMICAL
REACTIONS
LIQUID BYPRODUCT

In oxidizing acids, the cathode reaction

produces water:
 ELECTRODE POTENTIAL

When a pure metal is place in an electrolyte, an electrode

potential develops. This is related to the tendency of the
material to give up its electrons. The driving force for the
oxidation reaction is offset by an equal but opposite
driving force for the reduction reaction thus no net
corrosion occurs. Measuring electrode potential of a single
electrode material is not possible.
 ELECTROMOTIVE FORCE
SERIES
To determine the tendency of a metal to give up its electrons, we
measure the potential difference between the metal and a standard
electrode using a half-cell.
ELECTROMOTIVE FORCE
SERIES
 ELECTROMOTIVE FORCE
SERIES
The more negative the value of potential for the oxidation
of metal, the more electropositive is the metal; this means
the metal will have a higher tendency to undergo an
oxidation reaction.
CORROSION CURRENT
AND
POLARIZATION
 DEFINITION
CORROSION CURRENT Refers to the electric current generated during
the corrosion process of a metal. This current
arises because of the electrochemical
reactions that take place when a metal
interacts with its environment, such as water
or oxygen.

POLARIZATION
A change in the potential of an anode
or cathode, which in turn affects the
current in the cell.
ACTIVATION
Activation polarization refers to the energy
needed for reactions at the anode or cathode to
occur. Increasing polarization makes these
reactions harder, reducing the corrosion rate.
However, small differences in material
composition, structure, and segregation at the
electrodes can cause activation polarization to
vary, making it difficult to predict the corrosion
current.
CONCENTRATION
Concentration polarization occurs when ion
concentrations at the anode or cathode change
during corrosion, slowing down the reactions and
reducing the corrosion rate. For example, metal
ions may build up at the anode or hydrogen ions
may be depleted at the cathode. This polarization
is less effective when the electrolyte is highly
concentrated, heated, or agitated, as these
factors increase current density and accelerate
corrosion.
RESISTANCE
This type of polarization is caused by the
electrical resistivity of the electrolyte. If a
greater resistance to the flow of the current is
offered, the rate of corrosion is reduced. Again,
the degree of resistance polarization may change
as the composition of the electrolyte changes
during the corrosion process.
 TYPES OF
AND
PROTECTION AGAINST
ELECTROCHEMICAL CORROSION
 TYPES OF ELECTROCHEMICAL
CORROSION
UNIFORM ATTACK GALVANIC ATTACK
When a metal is placed in an Galvanic attack occurs when
electrolyte, some regions are certain areas always act as
anodic to other regions; anodes, whereas other areas
however, the location of these always act as cathodes. These
regions moves and even electrochemical cells are
reverses from time to time. called galvanic cells and can
Since the anode and cathode be separated into three types:
regions continually shift, the composition cells, stress cells,
metal corrodes uniformly. and concentration cells.
COMPOSITION
CELLS
Composition cells, or dissimilar metal corrosion,
occur when two different metals form an
electrolytic cell, causing one to corrode (anode)
and the other to be protected (cathode). The
galvanic series, which ranks metals and alloys
based on their anodic or cathodic behavior in
specific environments (e.g., seawater or
freshwater), is used to predict corrosion
tendencies more accurately than the emf series.
Intergranular corrosion
occurs when changes
at grain boundaries,
such as the
segregation of
impurities or
precipitation of a
second phase, create
a galvanic cell, making
the boundaries anodic
and prone to
corrosion.
STRESS CELLS
Stress cells develop when a metal contains
regions with different local stresses. The
most highly stressed or high-energy regions
act as anodes to the less-stressed cathodic
areas (Figure 23-8). Regions with a finer
grain size, or a higher density of grain
boundaries, are anodic to coarse-grained
regions of the same material. Highly cold-
worked areas are anodic to less cold-
worked areas.
Stress corrosion occurs due to galvanic
action and mechanisms like impurity
adsorption at crack tips, leading to
failure from combined corrosion and
applied stress. Higher stresses
accelerate failure. Similarly, corrosion
fatigue weakens materials by initiating
cracks (e.g., from pits or crevices) and
increasing crack propagation,
significantly reducing fatigue resistance.
CONCENTRATION CELLS
Concentration cells form when there are differences in electrolyte
concentration, causing varying electrode potentials. In an oxygen
concentration cell, areas with low oxygen act as the anode and
corrode, while areas with high oxygen act as the cathode. This leads
to pitting corrosion, such as rust under deposits or waterline
corrosion. In crevice corrosion, low oxygen concentrations at crack
tips cause the metal to corrode. Similarly, metal buried in soil or near
stagnant water may corrode due to differences in oxygen
concentration or soil composition, with the anodic areas corroding
more.
MICROBIAL
CORROSION
MICROBIAL-INDUCED CORROSION OCCURS WHEN FUNGI
AND BACTERIA CREATE CONDITIONS THAT ACCELERATE
ELECTROCHEMICAL CORROSION, ESPECIALLY IN
AQUEOUS ENVIRONMENTS. THESE MICROBES FORM
COLONIES ON METAL SURFACES, ALTERING THE
ENVIRONMENT AND INCREASING CORROSION RATES.
SOME BACTERIA PRODUCE SULFURIC ACID BY REDUCING
SULFATES, ATTACKING METALS LIKE STEEL, ALUMINUM,
AND COPPER, AS WELL AS CERAMICS AND CONCRETE.
PROTECTION AGAINST
ELECTROCHEMICAL
CORROSION
DESIGN
1. Prevent the formation of galvanic cells.
2. Make the anode area much larger than the
cathode area.
3. Design components so that fluid systems are
closed, rather than open, and so that stagnant
pools of liquid do not collect.
4. Avoid crevices between assembled or joined
materials (Figure 23-11).
5. The assembly should be designed in such a
manner that the corroded part can be easily and
economically replaced.
CONSIDER A COPPER-ZINC CORROSION COUPLE. IF THE CURRENT DENSITY AT THE COPPER CATHODE IS
0.05 A/CM^2, CALCULATE THE WEIGHT LOSS OF ZINC PER HOUR IF (1) THE COPPER CATHODE AREA IS 100
CM^2 AND THE ZINC ANODE AREA IS 1 CM^2 AND (2) THE COPPER CATHODE AREA IS 1 CM^2 AND THE
ZINC ANODE AREA IS 100 CM^2.
COATINGS
Coatings are used to protect metal
surfaces from corrosion by isolating
anode and cathode regions and
preventing the diffusion of oxygen or
water vapor.
CATHODIC
PROTECTION
Corrosion can be prevented by making the
metal a cathode, a method known as cathodic
protection. This can be done using a sacrificial
anode or impressed voltage. In sacrificial
protection, a more reactive metal (like zinc or
magnesium) is attached to the metal to be
protected, corroding instead of the metal and
supplying electrons. The sacrificial anode
eventually needs replacement.
PASSIVATION OR
ANODIC PROTECTION
Passivation is a process that slows down corrosion
by making a metal more cathodic. This is achieved
through anodic protection, where strong anodic
polarization prevents the usual anode reaction.
Passivation can be done by exposing the metal to
highly concentrated oxidizing solutions, like nitric
acid, which forms a protective hydroxide coating
on iron. Another method is increasing the anode
potential above a critical level, leading to the
formation of a passive film that reduces current
flow.
MATERIALS SELECTION AND
TREATMENT
Corrosion can be minimized by selecting the right
materials and applying specific heat treatments. In
castings, segregation can create localized galvanic cells
that accelerate corrosion, but homogenization heat
treatment can improve resistance.
 MICROBIAL DEGRADATION
AND
BIODEGRADABLE POLYMERS
MICROBIAL DEGRADATION
“Corrosion” of Polymers - attack by a variety
of insects and microbes.

Microbial - “microbe” which means

microorganisms such as bacteria, fungi, algae,
and viruses.

Polymers can be broken into low-molecular-

weight molecules by radiation or chemical
attack until they are small enough to be
ingested by the microbes.
Microbes - create enzymes that break down
the chemical bonds of polymers
Insects - Chew on polymers to create nests
or pathways, resulting in physical damage.
 Polymers Molecular Weight Degradation Process

Polyethylene, polypropylene,
and polystyrene (plastic
HIGH IMMUNE
bags, water bottles, food
containers, styrofoam)

polyesters, polyurethanes,
cellulosics, and plasticized
polyvinyl chloride (clothing LOW VULNERABLE
and fabrics, foam cushions,
flexible hoses and tube)
 BIODEGRADABLE
POLYMERS
Taking advantage of microbial attack on polymers.
Biodegradation requires the complete conversion
of the polymer to carbon dioxide, water, inorganic
salts, and other small byproducts produced by
bacteria's ingestion of the material.
Special polymers are produced to degrade
rapidly; a copolymer of polyethylene and starch is
one example.
Other polymers such as polycaprolactone (PCL),
polylactic acid (PLA), and polylactic glycolic acid
(PLGA) are useful in a number of biomedical
applications such as sutures and scaffolds.
 OXIDATION
AND
OTHER GAS REACTIONS
 OXIDATION AND OTHER GAS REACTIONS
Materials of all types may react with oxygen and other gases.
Alter the composition, properties, or integrity of a material.
Metals such as Al and Ti react with oxygen very readily.

OXIDATION OF METALS
Metals may react with oxygen to produce an oxide at the
surface.
Three aspects of this reaction: the ease with which the metal
oxidizes, the nature of the oxide film that forms, and the rate
at which oxidation occurs.
The ease with which oxidation occurs is given by the
standard free energy of formation for the oxide.
Y-axis-the thermodynamic
ELLINGHAM
tendency of a metal to react
with oxygen and form a stable
oxide.
DIAGRAM
X-axis - temperature (°C)
G° becomes less negative
(less favorable) at higher
temperatures because
thermal energy can
destabilize the oxide.
Metals lower on the diagram
(like Mg and Al) have a higher
thermodynamic tendency to
oxidize and form stable
oxides.
Metals higher on the diagram
(like Cu and Ni) oxidize less
readily because their ΔG°
values are closer to zero.
The nature of the oxide film can either result in a
protective or non-protective layer. Protective oxide
layers, such as aluminum oxide (Al₂O₃) or titanium oxide
(TiO₂), form stable, adherent coatings that prevent
further oxidation, while non-protective layers like iron
oxide (rust) can be porous and allow continued corrosion.
The rate at which oxidation occurs depends on
environmental conditions (temperature, moisture, and the
presence of salts or acids), the reactivity of the metal,
and the nature of the oxide layer. More reactive metals,
such as aluminum, oxidize faster, while noble metals like
copper form a protective copper oxide or patina over
time.
 PILLING-BEDWORTH (P-B)
RATIO

If P-B is less than 1, the oxide occupies a smaller

volume than the metal from which it formed; the
coating is, therefore, porous and oxidation continues
rapidly. (magnesium)
If the ratio is one to two, the volumes of the oxide
and metal are similar, and an adherent, non-porous,
protective film forms. (aluminum and titanium)
If the ratio exceeds two, the oxide occupies a large
volume and may flake from the surface, exposing
fresh metal that continues to oxidize. (iron)
(a) magnesium produces a porous oxide
film, (b) aluminum forms a protective,
adherent, nonporous oxide film, and (c)
iron forms an oxide film that spalls off
the surface and provides poor protection
OXIDATION AND THERMAL DEGRADATION OF
POLYMERS
Oxidation and Thermal Degradation of Polymers Polymers
degrade when heated and/or exposed to oxygen. A polymer
chain may be ruptured, producing two macroradicals.
In rigid thermosets, the macroradicals may instantly
recombine (a process called the cage effect), resulting in no
net change in the polymer.
In the more flexible thermoplastics—particularly for
amorphous rather than crystalline polymers—recombination
does not occur, and the result is a decrease in the molecular
weight, viscosity, and mechanical properties of the polymer.
OXIDATION AND THERMAL DEGRADATION OF
POLYMERS
Depolymerization continues as the polymer is exposed to
high temperatures.
Polymer chains can also unzip. In this case, individual
monomers are removed one after another from the ends of
the chain, gradually reducing the molecular weight of the
remaining chains.
As the degree of polymerization decreases, the remaining
chains become more heavily branched or cyclization may
occur. In cyclization, the two ends of the same chain may be
bonded together to form a ring.
The polymer becomes more brittle, less viscous, and loses its
functional properties.
OXIDATION AND THERMAL DEGRADATION OF
POLYMERS
Polymers also degrade by the loss of side groups on the
chain.
Chloride ions [in polyvinyl chloride (PVC)] and benzene rings
(in polystyrene) are lost from the chain, forming byproducts.
For example, as polyvinyl chloride is degraded, hydrochloric
acid (HCl) is produced. Hydrogen atoms are bonded more
strongly to the chains; thus, polyethylene does not degrade
as easily as PVC or polystyrene.
Fluoride ions (in TeflonTM) are more difficult to remove than
hydrogen atoms, providing TeflonTM with its high
temperature resistance.
 WEAR
AND
EROSION
 ADHESIVE WEAR
“scoring”, “galling”, or “seizing”
occurs when two solid surfaces slide over one another under
pressure.
Surface projections, or asperities, are plastically deformed
and eventually welded together by the high local pressures.
As sliding continues, these bonds are broken, producing
cavities on one surface, projections on the second surface,
and frequently tiny, abrasive particles— all of which
contribute to further wear of the surfaces.
If both surfaces have high hardnesses, the wear rate is low.
High strength, to help resist the applied loads, and good
toughness and ductility, which prevent the tearing of material
from the surface, may be beneficial.
Ceramic materials provide good adhesive wear resistance.
 ABRASIVE WEAR
When material is removed from a surface by
contact with hard particles, abrasive wear occurs.
The particles either may be present at the surface
of a second material or may exist as loose
particles between two surfaces
 ABRASIVE WEAR
This type of wear is common in machinery such as plows,
scraper blades, crushers, and grinders used to handle
abrasive materials and may also occur when hard particles
are unintentionally introduced into moving parts of
machinery. Abrasive wear is also used for grinding
operations to remove material intentionally. In many
automotive applications (e.g., dampers, gears, pistons,
and cylinders), abrasive wear behavior is a major concern.
Materials with a high hardness, good toughness, and high
hot strength are most resistant to abrasive wear.
quenched and tempered steels; carburized or surface-
hardened steels; cobalt alloys such as Stellite; composite
materials, including tungsten carbide cermets; white cast
irons; and hard surfaces produced by welding
 LIQUID EROSION
The integrity of a material may be destroyed by erosion
caused by high pressures associated with a moving liquid.
The liquid causes strain hardening of the metal surface,
leading to localized deformation, cracking, and loss of
material.
Cavitation occurs when a liquid containing a dissolved gas
enters a low pressure region. Gas bubbles form and grow.
When the liquid moves to a high-pressure area, these
bubbles collapse, creating a shock wave that generates
extremely high localized pressures. .
Liquid impingement occurs when liquid droplets carried in a
rapidly moving gas strike a metal surface. High localized
pressures develop because of the initial impact and the rapid
lateral movement of the droplets from the impact point along
the metal surface.
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