ELECTROPLATING AND

CORROSION

UNIT- 4
 ELECTROPLATING
• Electroplating (electro-deposition) defined as the production of metal
coatings on solid substrates by the action of an electric current.

• In contrast to various other process of applying coatings, electroplated

coatings are applied to improve appearance, corrosion resistance and
physicochemical properties of the surfaces (hardness, electrical and
thermal conductivity, solder-ability, reflectivity etc.).

• Some of the advantages of electroplated coatings over the other methods of

applying coatings are absence of an intermediate layer between the
coatings and the substrate metal as in the case of hot dip and diffusion
processes, fine structure and often very valuable physical properties
mentioned above and easy control of the coating thickness to fractions of a
micrometer.
 ELECTROPLATING
• Besides these, it is the most convenient method of applying
coatings of metals with high melting points such as copper,
nickel, chromium, iron, silver, gold and platinum (Noor Hisham,
1994).
• Electroplating is an electro-deposition process for producing a
dense, uniform, and adherent coating, usually of metal or alloys,
upon a surface by the act of electric current.
• The coating produced is usually for decorative and/or protective
purposes, or enhancing specific properties of the surface.
• The surface can be conductors, such as metal, or nonconductors,
such as plastics.
 ELECTROPLATING
• Electroplating products are widely used for many industries,
such as automobile, ship, air space, machinery, electronics,
jewelry, defense, and toy industries.
• The core part of the electroplating process is the electrolytic
cell (electroplating unit).
• In the electrolytic cell (electroplating unit) a current is passed
through a bath containing electrolyte, the anode, and the
cathode.
• In industrial production, pretreatment and posttreatment
steps are usually needed as well.
 ELECTROPLATING
• In general, electroplating process is divided into three stages i.e.
pretreatment, electroplating and post treatment.

• The nature of finish and design of the product dictate the procedures
to be adapted in order to produce quality finish.
 ELECTROPLATING
• The workpiece to be plated is the cathode (negative terminal).

• The anode, however, can be one of the two types: sacrificial anode
(dissolvable anode) and permanent anode (inert anode).

• The sacrificial anodes are made of the metal that is to be deposited.

• The permanent anodes can only complete the electrical circuit, but
cannot provide a source of fresh metal to replace what has been
removed from the solution by deposition at the cathode.

• Platinum and carbon are usually used as inert anodes.

 ELECTROPLATING
• Electrolyte is the electrical conductor in which current is carried by ions
rather than by free electrons (as in a metal).
• Electrolyte completes an electric circuit between two electrodes.
• Upon application of electric current, the positive ions in the electrolyte will
move toward the cathode and the negatively charged ions toward the
anode.
• This migration of ions through the electrolyte constitutes the electric
current in that part of the circuit.
• The migration of electrons into the anode through the wiring and an electric
generator and then back to the cathode constitutes the current in the external
circuit.
 ELECTROPLATING
• The metallic ions of the salt in the electrolyte carry a positive charge and are
thus attracted to the cathode.

• When they reach the negatively charged workpiece, it provides electrons to

reduce those positively charged ions to metallic form, and then the metal
atoms will be deposited onto the surface of the negatively charged
workpiece.

• Fig. 1 illustrates a typical plating unit for plating copper from a solution of
the metal salt copper sulfate (CuSO4).

• The cathode, which is the workpiece to be plated, is charged negatively.

• Some of the electrons from the cathode bar transfer to the positively charged
copper ions (Cu2+), setting them free as atoms of copper metal.
 ELECTROPLATING
• These copper atoms take their place on the cathode surface and
copper plate it.
• Concurrently, the same number of sulfate ions SO42+ is discharged
on the copper anodes, thereby completing the electrical circuit.
• In so doing, they form a new quantity of copper sulfate that
dissolves in the solution and restores it to its original composition.
• This procedure is typical of ordinary electroplating processes
with sacrificial anodes; the current deposits a given amount of
metal on the cathode and the anode dissolves to the same extent
(of the same electrical charge), maintaining the solution more or
less uniformly.
ELECTROPLATING
 ELECTROPLATING
• When a direct electric current passes through an electrolyte, chemical
reactions take place at the contacts between the circuit and the solution. This
process is called electrolysis.

• Electrolysis takes place in an electrolytic cell.

• Electroplating is one specific type of electrolysis.

• Besides electroplating, electrolysis has also been widely used for

preparation of halogens and notably chlorine, and refining of metals,
such as copper and zinc.

• Understanding the electrochemical principles of electrodeposition is

essential to the development of electroplating technologies.
 ELECTROPLATING
Oxidation/Reduction

• In a wider sense, all electron-transfer reactions are considered oxidation-reduction.

• The substance gaining electrons (oxidizing agent, or oxidant) oxidizes the substance that is
losing electrons (reducing agent, or reductant).

• In the process, the oxidizing agent is itself reduced by the reducing agent. Consequently, the
reduction process is sometimes called electronation, and the oxidation process is called ‘‘de-
electronation.’’

• Because a cathode is attached to the negative pole of the electric source, it supplies electrons
to the electrolyte.

• On the contrary, an anode is connected to the positive pole of the electric source; therefore, it
accepts electrons from the electrolyte.

• Various reactions take place at the electrodes during electrolysis. In general,

reduction takes place at the cathode, and oxidation takes place at the anode.
 ELECTROPLATING
Anode and Cathode Reactions

• Electrodeposition or electrochemical deposition (of

metals or alloys) involves the reduction of metal ions from electrolytes.

• At the cathode, electrons are supplied to cations, which migrate to the anode.

• In its simplest form, the reaction in aqueous medium at the cathode follows the equation:

with a corresponding anode reaction.

• At the anode, electrons are supplied to the anions, which migrate to the anode. The anode
material can be either a sacrificial anode or an inert anode. For the sacrificial anode, the
anode reaction is:

In this case, the electrode reaction is electrodissolution that continuously supplies the metal ions.
 ELECTROPLATING
Faraday’s Laws of Electrolysis

• In 1833, the English scientist, Michael Faraday, developed Faraday’s laws of

electrolysis.

• Faraday’s first law of electrolysis and Faraday’s second law of electrolysis state that

the amount of a material deposited on an electrode is proportional to the amount of

electricity used.

• The amount of different substances liberated by a given quantity of electricity is

proportional to their electrochemical equivalent (or chemical equivalent weight).

• In the SI system, the unit quantity of electricity charge and the unit of electric charge

are coulomb (C); one coulomb is equivalent to one ampere flowing for one second

(1 C = 1 A sec).
 ELECTROPLATING
• The electrochemical equivalent of an element is its atomic weight divided by the valence

change involved in the reaction.

• For example, for the reaction, Fe2+ → Fe0, the valence change is 2, and the electrochemical

equivalent of iron is 55.85/2 = 27.925 in this reaction.

• Depending on the specific reaction, one element may have different equivalent weights,

although it has only one atomic weight.

• In detail, to reduce one mole of a given metal from a metal ion with the valence charge of n+,

n moles of electrons are required.

• That is, the total cathodic charge used in the deposition, Q(C), is the product of the number of

gram moles of the metal deposited, m, the number of electrons taking part in the reduction, n,

Avogadro’s number, Na (the number of atoms in a mole), and the electrical charge per

electron, Qe(C).
 ELECTROPLATING
• Thus, the following equation gives the charge required to reduce m moles of metal:

• The product of the last two terms in this Eq. is the Faraday constant, F.

• Therefore, the number of moles of the metal reduced by charge Q can be obtained
as:

• The Faraday constant represents the amount of electric charge carried by 1 mol, or
the Avogadro’s number of electrons.

• The Faraday constant can be derived by dividing Avogadro’s number, or the number
of electrons per mole, by the number of electrons per coulomb.

• The former is approximately equal to 6.02 x1023 and the latter is approximately 6.24
x1018. Therefore,
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 ELECTROPLATING
 Current Efficiency, Current Density, and Current Distribution
Faraday’s laws give theoretical prediction of electrodeposition in an ideal situation.
In a real application, many factors influence the coating quantity and quality.
 Current efficiency
 It is stated in Faraday’s laws that the amount of chemical charge at an electrode is
exactly proportional to the total quantity of electricity passing.
 However, if several reactions take place simultaneously at the electrode, side
reactions may consume the product.
 Therefore, inefficiencies may arise from the side reactions other than the intended
reaction taking place at the electrodes.
 Current efficiency is a fraction, usually expressed as a percentage, of the current
passing through an electrolytic cell (or an electrode) that accomplishes the desired
chemical reaction. Or,
 ELECTROPLATING

Current density:-
• Current density is defined as current in amperes per unit area of the
electrode.
• It is a very important variable in electroplating operations.
• It affects the character of the deposit and its distribution.
 ELECTROPLATING
• Current distribution:-
• The local current density on an electrode is a function of the position
on the electrode surface.
• The current distribution over an electrode surface is complicated.
• Current will tend to concentrate at edges and points, and unless the
resistance of the solution is very low, it will flow to the workpieces
near the opposite electrode more readily than to the more distant
workpieces.
• It is desired to operate processes with uniform current distribution.
• That is, the current density is the same at all points on the electrode
surface.
 ELECTROPLATING
Overpotential and overvoltage

• The equilibrium is dynamic with metal ions being discharged and metal atoms

being ionized, but these two effects cancel each other and there is no net change in

the system.

• For the realization of metal deposition at the cathode and metal dissolution at the

anode, the system must be moved away from the equilibrium condition.

• An external potential must be provided for the useful electrode reactions to take

place at a practical rate; this external potential may have several causes.

• . Overpotential is the difference in the electrode potential of an electrode

between its equilibrium potential and its operating potential when a current is

flowing.
 ELECTROPLATING
• The overpotential represents the extra energy needed to force the electrode reaction to

proceed at a required rate (or its equivalent current density).

• Consequently, the operating potential of an anode is always more positive than its equilibrium

potential, while the operating potential of a cathode is always more negative than its

equilibrium potential.

• The overpotential increases with increasing current density.

• The value of the overpotential also depends on the inherent speed of the electrode reaction.

• A slow reaction (with small exchange current density) will require a larger overpotential for a

given current density than a fast reaction (with large exchange current density).

• Overpotential is also referred to as polarization of the electrode.

• An electrode reaction always occurs in more than one elementary step, and there is an

overpotential associated with each step. Even for the simplest case, the overpotential is the

sum of the concentration overpotential and the activation overpotential

 ELECTROPLATING
 Overvoltage is the difference between the cell voltage (with a current flowing) and

the open-circuit voltage (OCV).

 The overvoltage represents the extra energy needed to force the cell reaction to

proceed at a required rate.

 Consequently, the cell voltage of an electrolytic cell is always more than its OCV,

while the cell voltage of a galvanic cell (e.g., a rechargeable battery during

discharging) is always less than its OCV.

 Occasionally, it is also referred to as polarization of the cell.

 The overvoltage is the sum of the overpotentials of the two electrodes of the cell

and the ohmic loss of the cell.

 Unfortunately, the terms overvoltage and overpotential are sometimes used

interchangeably.
 ELECTROPLATING
SURFACE PREPARATION
• Workpieces to be plated may be put through a variety of pretreating processes, including
surface cleaning, surface modification, and rinsing.

• The purpose of surface pretreatment is to remove contaminants, such as dust and films,
from the substrate surface.

• The surface contamination can be extrinsic, composed of organic debris and mineral dust
from the environment or preceding processes. It also be intrinsic, such as a native oxide
layer.

• Contaminants and films interfere with bonding, which can cause poor adhesion and even
prevent deposition.

• Therefore, surface pretreatment is important to ensure plating quality.

• Most (metal) surface treatment operations have three basic steps: surface cleaning, surface
treatment, and rinsing.
 ELECTROPLATING
Surface Cleaning:-
• Cleaning methods should be able to minimize substrate damage while
removing the contaminants, dust, film, and/or debris.
• Cleaning processes are based on two approaches: chemical approach and
mechanical approach.
1. Chemical approaches
A chemical approach usually includes solvent degreasing, alkaline
cleaning, (soak cleaning), and acid cleaning (acid pickling).
 Solvent Degreasing. Contaminants consist of oils and grease of various
types, waxes, and miscellaneous organic materials.
• These contaminants can be removed by appropriate organic solvents, either
by dipping the workpieces in the solvent or by vapor decreasing.
 ELECTROPLATING
 Alkaline Cleaning:- Workpieces are immersed in tanks of hot alkaline cleaning solutions to
remove dirt and solid soil.

• A special type of alkaline cleaning is electrocleaning. In electrocleaning, the workpiece can

be either the cathode (namely direct cleaning) or the anode (reverse cleaning).

 Acid Cleaning:- Acid cleaning can move heavy scale, heat-treat scale, oxide, and the like.
The most commonly used acids include sulfuric and hydrochloric.

2. Mechanical approaches
• Mechanical preparations include polishing, buffing, and some variations.

• Polishing is to remove small amounts of metal by means of abrasives. It produces a surface

that is free of the larger imperfections left by grinding, and is a preliminary to buffing.

• Buffing is similar to polishing, but uses finer abrasives to remove very little metal.

• Buffing can produce an extremely smooth surface.

 ELECTROPLATING
Surface Modification:-
• Surface modification includes change in surface attributes, such as application of
(metal) layer(s) and /or hardening.

Rinsing:-
• In wet plating, when workpieces are transferred from one treating solution to
another, or when they leave the final treating solution, they carry some of the
solution in which it has been immersed. This solution is called drag-out.

• In most cases, this residue solution should be removed from the workpieces surface
by rinsing before the workpieces enter the next step in sequence, or come out of the
final processing solution.

• The dirty rinse water will be sent to the wastewater treatment facilities before
being discharged to a public sewage system.
 ELECTROPLATING
ELECTROLYTIC METAL DEPOSITION

• There are three types of electrolytic metal deposition processes: direct

current electrodeposition, pulse plating, and laser-induced metal
deposition.

 Direct Current Electrodeposition

 In the direct current (DC) electrodeposition, the current source is a power

source in the form of a battery or rectifier (which converts alternating
current electricity to regulated low-voltage DC current) provides the
necessary current.

 Electroplating is performed in a plating unit.

 Electrodes, immersed in the electroplating bath (electrolyte), are

connected to the output of a DC current source.
 ELECTROPLATING
 Pulse Plating

• Electrodeposition using pulsed currents is known as pulse plating.

• The pulsed currents can be unipolar (on–off) or bipolar (current reversal).

• Pulses can be used along or be superimposed on a DC feed.

• By using the bipolar pulse, metal deposition occurs in the cathodic pulse period, with a limited amount of

metal being redissolved in the anodic period.

• This repeated deposition and partial redissolution could improve the morphology and the physical

properties of the deposit.

 Laser-Induced Metal Deposition

 In laser-induced metal deposition, a focused laser beam is used to accelerate the metal deposition.

 Experiments have shown that the deposition rate can be increased by 1000 times.

 The plating equipment mainly consists of a laser head with focusing optics and the electrolytic cell.

 The focused laser beam can pass through a hole in the anode through the electrolyte and impinge on the

cathode surfaces.
 ELECTROPLATING
ELECTROLYTE

• Different metals may need different types of electrolyte.

• The composition and properties of the electrolyte is very important for the coating quality.

• Types of electrolytes include water solutions of acids, bases, or metal salts, certain pure
liquids, and molten salts. Gases may act as electrolytes under conditions of high temperature
or low pressure.

• In addition to metal salts, electrodeposition electrolytes usually contain a number of additives

for various purposes.

• Some agents are used to increase electrolyte conductivity (supporting electolytes).

• Others may be used for increasing bath stability (stabilizers), activating the surface
(surfactants or wetting agents), improving leveling or metal distribution (leveling agents),
or optimizing the chemical, physical, or technology properties of the coating.

• These coating properties include corrosion resistance, brightness or reflectivity, hardness,

mechanical strength, ductility, internal stress, wear resistance, or solderability.
 ELECTROPLATING
TYPES OF ELECTROPLATING PROCESSES

• Depending on the size and geometry of the workpieces to be plated, different plating
processes, including mass plating, rack plating, continuous plating, and in-line
plating, may be adopted.

Mass Plating

• Mass plating is used for small workpieces to be plated in large quantities, such as
nuts and bolts, but it is not used for delicate workpieces.

• The most widely used mass plating system is called barrel plating, where the
workpieces are loaded into a plating barrel.

• Other mass plating containers include plating bells and vibratory units.
 ELECTROPLATING
Rack Plating
• Some workpieces cannot be mass plated because of their size, shape, or
special features.
• Rack plating means workpieces are mounted on a rack for the appropriate
pretreatment plating and posttreatments.
• Racks are fixtures suitable for immersion in the plating solution.
• Rack plating is sometimes called batch plating.
Continuous Plating
• Continuous plating means the workpieces to be plated move continuously
passing either one row or between two rows of anodes. Continuous plating is
usually used for a workpiece of simple and uniform geometry, such as metal
strip, wire, and tube.
 ELECTROPLATING
In-Line Plating

• In-line plating is used to integrate the plating and finishing processes into a main production line.

• The benefit of in-line plating includes exclusion of pretreatment steps and a significant reduction in
material, chemical and energy consumption, and waste discharge.

TYPES OF METAL COATINGS

• Plating metals can be roughly classified into the following categories with the typical applications.

Sacrificial Coatings

• Sacrificial coatings are primarily used for the protection of the base metal, usually iron and steel.
Another name for sacrificial coating is anodic coating, because the metal coatings are anodic to the
substrate metal, so the coatings sacrifice themselves to protect the base metal from corrosion.

• Zinc (Zn) and cadmium (Cd) coatings can be used as sacrificial coatings.

• Because of high toxicity, cadmium plating is now forbidden by law in many countries.
 ELECTROPLATING
Decorative Protective Coatings

• Decorative protective coatings are primarily used for adding an attractive appearance to some

protective qualities.

• Metals in this category include copper (Cu), nickle (Ni), chromium (Cr), zinc (Zn), and tin

(Sn).

Engineering Coatings

• Engineering coatings (sometimes called functional coatings) are used for enhancing specific

properties of the surface, such as solderability, wear resistance, reflectivity, and conductivity.

• Metals for engineering purpose include precious gold (Au) and silver (Ag), six platinum

metals, tin, and lead (Pb). The six platinum metals are ruthenium (Ru), rhodium (Rh),

palladium (Pd), osmium (Os), iridium (Ir), and platinum (Pt).

• These six metals are noble, i.e., with positive electrode potentials and they are relatively inert.
 ELECTROPLATING
Minor Metal Coating

• Minor metals here refer to iron (Fe), cobalt (Co), and indium (In). They are easily plated but

have limited applications in electroplating.

Unusual Metal Coating

• The unusual metals are rarely electroplated and can be divided into the following categories:

1) easily platable from aqueous solutions but not widely used, such as arsenic (As), antimony

(Sb), bismuth (Bi), manganese (Mn), and rhenium (Re); 2) platable from organic electrolyte

but not aqueous electrolyte, such as aluminum (Al); and 3) platable from fused-salt

electrolyte but not aqueous electrolyte, including refractory metals (named because of their

relatively high melting points), such as titanium (Ti), zirconium (Zr), hafnium (Hf),

vanadium (V), niobium (Nb), tantalum (Ta), molybdenum (Mo), and tungsten (W). The

periodic table in Fig. 3 shows that the metals that can be electrodepos- F3ited from aqueous

solutions are those inside the frame.

 ELECTROPLATING
• Alloy Coatings

An alloy is a substance that has metallic properties and is composed of two or more chemical

elements, at least one of which is a metal. The elements composing the alloy are not

distinguishable by the unaided eye. Examples of alloy coating include gold–copper–

cadmium, zinc–cobalt, zinc–iron, zinc–nickle, brass (an alloy of copper and zinc), bronze

(copper–tin), tin–zinc, tin–nickle, and tin–cobalt. Alloy coatings are produced by plating two

metals from the same solution.

Multilayered Coatings

• Multilayered coatings are produced by plating different metals from the same solution at

different potentials. A pulse train-shaped potential is enforced, resulting in the multilayer

deposition. For example,

multilayered coatings based on copper, nickle, chromium, in that order, can be applied to

either metal or plastic components for visual appearance, corrosion and wear resistance, and

weight saving.
 ELECTROPLATING
Composite Coatings
• Composite materials can be defined as coatings consisting of minute second-phase
particles dispersed throughout a metal matrix.
• The size of the second phase particles may range from 10 mm down to nanoscale
and the particles can be inorganic, organic, or occasionally metallic.
• The presence of fine particles in a metal matrix generally improves its mechanical
and chemical properties, resulting in a wide range of applications.Composite
coatings with an electrodeposited metal matrix and nonmetallic inclusions have
excellent wear resistance and permit emergency dry running of machinery.
Conversion Coatings
• Conversion coatings are formed by a reaction of the metal on the surface of the
substrate with a solution.
• For example, chromate coatings are formed by the reaction of water solutions of
chromic acid or chromium salts.
• The chromate coatings can be applied to aluminum, zinc, cadmium, and magnesium.
• The coatings usually have good atmospheric corrosion resistance. Chromate
coatings are widelyused inprotecting common household products, such as screws,
hinges, and many hardware items with the yellow-brown appearance.
 ELECTROPLATING
Anodized Coatings

• Anodizing is produced by electrochemical conversion.

• In an anodizing process, the metal workpiece to be plated is the anode in a suitable

electrolyte.

• With the electric current passing through the electrolyte, the metal surface is converted to a

form of its oxide.

• An anodizing process is usually used on aluminum for protection and cosmetic purposes.

• The electrolyte provides oxygen ions that react with metal ions to form the oxide, and

hydrogen is released at the metal or carbon cathode.

• Anodizing differs from electroplating in two aspects. In electroplating, the workpiece to be

plated is the cathode, and the metallic coatings are deposited

on the workpiece. In anodizing, the workpiece is the anode, and its surface is converted to a

form of its oxide.

 Corrosion of Metals
 Corrosion (from Latin corrodere, “gnaw to pieces”) of metals is the spontaneous chemical

(oxidative) destruction of metals under the effect of their environment.

 Most often it follows an electrochemical mechanism, where anodic dissolution (oxidation)

of the metal and cathodic reduction of an oxidizing agent occur as coupled reactions.

 Sometimes a chemical mechanism is observed.

 Corrosion (rusting) of metals is causing huge losses to the economy.

 This process affects the metal structures of buildings and bridges, the equipment of

chemical and metallurgical plants, river and sea vessels, underground pipelines, and

other structures.

 In the United States, for instance, corrosion-related losses approach a figure of $100 billion

per year, which is almost 5% of the gross national product.

 Corrosion of Metals
• Direct losses attributable to corrosion include expenditures for the
replacement of individual parts, units, entire lines or plants, and for various
preventive and protective tasks (such as the application of coatings for
corrosion protection).

• Indirect losses arise when corroded equipment leads to defective products

that must be rejected; they also arise during downtime required for
preventive maintenance or repair of equipment.

• About 30% of all steel and cast iron are lost because of corrosion.

• Part of this metal can be reprocessed as scrap, but about 10% is irrevocably
lost.
 Corrosion of Metals
• The significance of corrosion protection has risen sharply in
recent years for a number of reasons:

(1) because of efforts to reduce the metal content of parts (e.g., by

using thinner metallic support structures);

(2) with the use of new types of equipment and processes involving
expensive equipment operated under extreme conditions, such as
nuclear reactors and jet and rocket engines; and

(3) in connection with the development of products having extremely

thin metal films, such as printed circuit boards and integrated
circuits.
 Corrosion of Metals
VARIOUS TYPES OF CORROSION

• Corrosion phenomena can be classified according to the type of corroding medium

acting on the metal.

• Corrosion in nonelectrolytic media is distinguished from that in electrolytic media.

• The former include dry hot gases, organic liquids (e.g., gasoline), and molten metals.

• Electrolytic media are most diverse, and include ambient air (with moisture and other

components), water (seawater, tap water) and aqueous solutions (acids, alkalies, salt

solutions), moist soil (for underground pipelines, piles, etc.), melts, and nonaqueous

electrolyte solutions.

• Corrosion phenomena can also be classified according to the visible aspects of corrosive

attack.
 Corrosion of Metals
• This may be general (continuous), affecting all of the exposed surface of a
metallic object, or localized. General corrosion can be uniform and nonuniform.

• Depending on the width and depth of the segments affected by localized

corrosion, we may speak of spot, pit (large or small), or subsurface corrosion.

• Often, intercrystalline corrosion is encountered, which propagates in the zones

between individual metal crystallites.

• Cracks develop between or in individual crystals in the case of stress corrosion

cracking.

• Certain types of corrosion are selective.

• Thus, corrosion cracking is observed primarily in the case of alloys and only
when these are in contact with particular media.
 Corrosion of Metals
• Other factors are fretting and cavitation in a liquid (impact of the liquid).

• Corrosion can also occur due to electric currents (stray currents in soils).

• Almost all metals are subject to corrosion, an exception being the noble
metals (the platinum metals, gold, silver) which under ordinary conditions
do not corrode.

• Corrosion of iron is the most prominent problem since parts and structures
consisting of iron and steels are used so widely.

• Different parameters are used to characterize the corrosion rate: the loss
of mass by the metal sample within a certain length of time (per unit area),
the decrease in sample thickness, the equivalent electric current density,
and so on.
 Corrosion of Metals
MECHANISMS OF CORROSION PROCESSES

• The analysis of corrosion processes comprises examining the special

features in a given metal’s anodic dissolution, establishing the nature
of the cathodic reaction (which is coupled with metal dissolution), and
defining in greater detail the loci of the anodic and cathodic partial
reaction.

• In corrosion, the equilibrium potential of reduction of the oxidizing

agent is always more positive than that of dissolution of the metal (at
the given solution composition).

• The main cathodic reactions in metal corrosion are hydrogen

evolution and the reduction of dissolved oxygen.
 Corrosion of Metals
• It is only in special cases when the corresponding reactants are
available that chlorine, nitric acid, or other oxidizing agents will be
reduced.
• Hydrogen evolution occurs at much more negative potentials than
oxygen reduction.
• Hence, corrosion coupled with hydrogen evolution can be observed
only for metals having sufficiently negative equilibrium potentials—
the alkali and alkaline-earth metals, aluminum, magnesium, zinc, iron,
and so on—and is encountered predominantly in acidic and alkaline
media.
• Oxygen-depolarized corrosion occurs in contact with air, most often in
neutral solutions (atmospheric corrosion, waterline corrosion in
seawater, etc.).
 Corrosion of Metals
CORROSION PROTECTION

• Electrochemical and nonelectrochemical ways to protect metals against corrosion can be

distinguished.

• The nonelectrochemical ways include dense protective films that isolate the metal against
effects of the medium and may be paint, polymer, bitumen, enamel, and the like.

• Electrochemical methods of protection rest on different precepts:

(1) electroplating of the corroding metal with a thin protective layer of a more corrosion-
resistant metal,

(2) electrochemical oxidation of the surface or application of other types of surface layer,

(3) control of polarization characteristics of the corroding metal (the position and shape of
its polarization curves), and

(4) control of potential of the corroding metal.

 Corrosion of Metals
• The polarization characteristic of a corroding metal can be
controlled by various additives to the solution, called corrosion
inhibitors, which adsorb on the metal and lower the rates of the
cathodic and/or anodic reaction.

• Inhibitors are used primarily for acidic electrolyte solutions,

sometimes also for neutral solutions.

• Various organic compounds with –OH, –SH, –NH2, –COOH, and

so on, as the functional groups are used as inhibitors.

• This inhibitor markedly lowers the rate of both the anodic and
cathodic processes.
 Corrosion of Metals
• Sometimes anodic protection is used, in which case the metal’s potential is made
more positive.

• The rate of spontaneous dissolution will strongly decrease, rather than increase,
when the metal’s passivation potential is attained under these conditions.

• To make the potential more positive, one must only accelerate a coupled cathodic
reaction, which can be done by adding to the solution oxidizing agents readily
undergoing cathodic reduction (e.g., chromate ions).

• The rate of cathodic hydrogen evolution can also be accelerated when minute
amounts of platinum metals, which have a strong catalytic effect, are incorporated
into the metal’s surface layer.