1.

1 Definition of Corrosion
Corrosion is the degradation of a material, usually a metal, by chemical or electrochemical reaction with its environment. Or simply, Corrosion is extractive metallurgy in reverse.
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1.2 The Co$t of Corrosion

Direct Cost: ~ 4.2% GNP

Replacement of corroded components Use of corrosion resistant alloys Use of coatings or inhibitors Electrochemical protection measures

Indirect Cost

Loss of production during downtime Loss of products due to leakage Loss of efficiency due to corrosion Contamination Loss of human lives due to explosion, fire etc.

1.3 Corrosion can be controlled

Materials selection Proper design Electrochemical protection Inhibitors Paints/Coatings

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1.4 Significance of Corrosion Control

Economics Safety Environmental concerns

1.5 Summary of this lecture

This lecture presents an overview of corrosion and its technological and sociological effects on our society. The interaction of a material with its environment results in CORROSION. The high cost to a nation's economy due to corrosion can be reduced by 25% if existing corrosion control technology is used. The significance of corrosion control are economics, safety and environmental concerns.

1.6 Reading assignments

2. Enabling Theory for Aqueous Corrosion

Energy: the Rule of Law Matters of Substance Processes in Solution Metals: Might and Blight Metals in the Melting Pot Defects in Metal Structures Electrical Science Summary of this lecture Reading assignments

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2.1 Energy: the Rule of Law

The law: energy can neither be created nor destroyed. The Rule: all spontaneous changes occur with a release of free energy from the system to the surroundings at constant temperature and pressure. Points to note:

corrosion is a spontaneous process. free energy is released in the process. metals returned to its stable state.

In nature:

water runs downhill hot coffee go cold spinning tops slow down

The driving force for corrosion reaction: chemical energy - energy stored in chemical bonds of substances -internal energy. Free energy: the portion of internal energy available for powering engines or causes corrosion reaction. Transition state theory concerns A+ B= AB= C + D The transition sate must be of higher free energy than the sum of the free energies of the separate species. The rate of corrosion reaction

The quantity in square brackets is a measure of the amount of substance. This will be explained in the next section. The rate constant can be shown to be related to the size of the free energy barrier:

where C and R are constants, and T is the absolute temperature. Inspection of the equation shows that as T increases, so also does the rate constant (and hence the rate) but when the size of the barrier ( ) is increased, the rate constant decreases. Eqn. (2.3) is a modified form of an important equation called the Arrhenius equation, named after the scientist who first described this successful theory. Now consider the reverse process. Overall, it cannot be spontaneous, because there is an increase in free energy upon conversion of C and D into A and B. Furthermore, there is a bigger free energy barrier for the new reactants, C and D, to cross. The Transition State Theory says that the reverse process is possible, but occurs at a much reduced rate, represented by an equation similar to eqn. (2.3) in which the activation free energy has been increased from to ( + ), as in Fig. 2.1. The reverse process is possible only on the molecular scale where the energies of an individual C and D pair may be such as to allow the formation of the transition state. (Remember that our rule applies to an overall free energy change for a bulk system.) The reverse process occurs at a rate far less than the rate of the forward process, so the net reaction observed on the large scale will always appear to be a steady conversion of A + B into C + D. For

the reverse process to occur in the bulk system, energy must be supplied to the system (e.g. in electrolysis). The use of energy profiles is of considerable assistance in the understanding of corrosion processes and will be frequently used throughout our discussions of corrosion theory. We shall now progress to a description of substances.
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2.2 Matters of Substance

Fact: 103 elements have been discovered; Five of the 103 elements: oxygen, silicon, aluminum, iron and calcium make up 91% of the matter in the earth's crust. The amounts of oxygen and silicon together make 74.3% of the mass. Of the 103 elements, the great majority are metals. amount of substance: One mole of a substance is the molecular weight of that substance expressed in grams. One mole of material A and one mole of material B have equal numbers of molecules but different masses. Three ways of atoms may combine:

by sharing electrons to form covalent bonds; by exchanging electrons to form ionic bonds; by sharing electrons to form metallic bonds.

By losing an electron, the atom is ionized. Cation: the ion with a net positive charge. By gaining an electron, the atom is ionized. Anion: the ion with a net negative charge. Oxidation reaction is related to

anodic reaction lose electrons anode

Reduction reaction is related to

cathodic reaction gain electrons cathode

M = Mn+ + ne- fundamental definition of corrosion:

corrosion is the degradation of a material by an electrochemical reaction with its environment.
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2.3 Process in Solution

Dissociation of water into hydrogen ions and hydroxyl ions:

H2O = H+ + OH- (2.8)

Law of mass action: For equilibrium process

applying law to equilibrium reaction (2.8):

[H+].[OH-] = constant Under standard conditions: 25oC, 1 atmosphere, [H+].[OH-] = 10-14

pH= - log[H+] pOH = -log[OH-] pH + pOH = 14

Scales of pH and pOH

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2.4 Metals: Might and Blight

mechanical engineers structural engineers and designers

are always more than willing to exploit the might of metals, corrosion engineer are required to patch up the blight of corrosion. A profitable career ??? Properties of metals:

opaque and lustrous ductility high strength/weight ratio conductivity (heat & electric)

Metals are extremely important in modern engineering yet many are susceptible to corrosion. What makes them so useful yet so vulnerable ?
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2.5 Metals in the Melting Pot

Solidification process determines:

the mechanical property corrosion resistance property

A typical cooling curve for the solidification of a metal. Alloys show similar behaviour with discontinuities at B and C (known as 'arrests') but which are not at the same temperature. Effect of cooling rate on

structure and property A2 experiment recalled

Rapid cooling causes many nucleation sites; slow cooling yields a few crystals. Dendrite: a branched crystal Dendritic growth: process of solidification to form dendrite. Grains: individual crystals Grain boundaries: zones between any two grains

Fig.2.4 Dendritic growth and solidification: (a) nucleation of crystals in the melt; (b) growth of crystals into dendrites; (c) complete solidification; and (d) final grain structure.
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2.6 Defects in Metal Structures

Imperfections in the lattice structures of metals known as defects, have a considerable effect on the corrosion resistance properties. Types of defects occur within the grains:

1. Point defects: single atom defect

vacancies - a missing atom substitutional defects a foreign atom interstitial defects a squeezed atom

2. Line defects: -planes of atoms not perfectly fitted into the lattice(dislocations)

edge dislocations screw dislocation 3. Volume defects voids: holes in the materials cracks introduced during processing inclusions particles of foreign matter embedded in the solid.

Volume defects play an important role in corrosion mechanisms.

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2.7 Electrical Science

Electricity: passage of the charged particles between two defined points. Current: the flow of electrons Resistance: opposition to the flow of electrons

A: cross sectional area l: length of conductor p: resistivity/specific resistance Conductance: the reverse of resistance Types of electric conductors:
1. 2. 3.

metallic conductors: have electronic conductance. electrolytic conductors: have ionic conductance semiconductors: have both electronic and ionic conductance

Directions: in corrosion cells: electrons flow from anode to cathode in the metallic conductor. current flows from cathode to anode in the metallic conductor. current flows from anode to cathode in the electrolyte (ionic conductor).

in a battery: positive and negative poles are used. the use of anode and cathode are not recommended.

Electromotive force E. M. F.series: driving force (electrochemical potential) from a cell. Volts = Amperes x Ohms V=IR Coulombs = Amperes x seconds
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2.8 Summary
In this lecture, we discussed some of the enabling theories for aqueous corrosion. The basic concepts covered are: chemical, metallurgical and electrical in nature. As the interaction between a material with its environment is affected by both the chemical parameters associated with the environment (pH, temperature, flow rate, dissolved gases etc.) and the metallurgical factors associated with the material (processing conditions, heat history, defects and inclusions etc), it is not difficult to realize that the environment is just as important as the material in the context of corrosion.

Lecture 3: The Theory for Aqueous Corrosion (I)

Thermodynamic Aspects of Corrosion Reactions The Nernst Equation Basic Wet Corrosion Cell

Standard Electrode Potential Summary Reading Assignments

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4.1 Thermodynamic Aspects of Corrosion Reactions

For most metals, the chemically combined states are preferred by nature:

oxides sulphides carbonates other complex compounds

Ores are in low energy states (stable states) Nature is always concerned with minimizing energy. Metals extracted from their ores and are in high energy states, thermodynamically, they are not stable. Corrosion is a natural occurring process, predicted by thermodynamics laws. high energy states (metal) = low energy states (metals compounds) It is this tendency of metals to recombine with elements presents in the environments that leads to the phenomenon known as Corrosion. Corrosion is the degradation of a metal by an electrochemical reaction with its environment. Points to note: The low energy corrosion product is not the same as an ore (may be similar), the energies of the ore and the corrosion product may well be comparable. Tendency to corrode and rate of corrosion Tendency to corrode is determined by the free energy difference and its corrosion product. between a metal

Rate of corrosion is determined by the size of the energy barrier (the free energy of activation, G*) The rate constant kcorr =A exp (-G*/RT)

A= undefined constant; R= gas constant, T= absolute temperature Rate of corrosion reaction = kcorr [reactants] Points to note about G*: G* is the minimum amount of energy required to drive the molecules/atoms over the activation energy barrier, so that appreciable reaction can take place. Free energy is the single factor to determine the possibility of a corrosion reaction. All interactions between elements and compounds are governed by the free energy changes available to them. For a spontaneous transition from high energy (initial state, Gi) to low energy (final state, Gf), the free energy change = Gf - Gi < 0 (negative) For a spontaneous reaction to occur, Points to note: At room temperature, most chemical compounds of metals have lower energy than the uncombined metals. must be negative !

Most metals have an inherent tendency to corrode.

Why do gold, platinum and other precious metals not corrode ?

the energetics may not be favorable the size of activation energy may be too great (the rate is extremely

slow) Thermodynamic data alone tells us that copper and magnesium are expected to corrode naturally In wet, aerated atmosphere. Exceptions: Iron objects preserved after centuries of immersion at the bottom of peat bogs. There may always be special circumstances why corrosion does not occur when expected. For a reaction: A + B = C = D, the free energy change, thermodynamic equation , where J is the reaction quotient. , is given by

At equilibrium condition, J=K, where K is the equilibrium constant.

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Nernst equation
The free energy change is related to electrical potential by Faraday's law:

Where, F=Faraday constant, 96,500 coulombs/mole; z number of electrons transferred in the corrosion reaction and E is the measured potential in volts. Under standard conditions, Go = -zFEo From G = Go + RTln{[C][D]/{[A][B]}, we have - zFE= -zFEo + RTln{[C][D]}/{[A][B], the Nernst equation:

E= Eo - (RT/zF)ln{[[C][D]}/{[A][B]}
This is one of the most fundamental equations in corrosion science and engineering. Under standard conditions: T=298k, R=8.3143 J (mol k)-1, Nernst equation can be written as

E= Eo - (0.059/z)lg{[Products]/[Reactants]}
E is the non equilibrium potential generated by the corrosion reaction; [reactants] = concentration of reactants and [products] = concentration of products. At equilibrium conditions, E=0 [Back to Top]

4.2 The Basic Wet Corrosion Cell

Four essential components of a corrosion cell

The Anode The Cathode The Ionic Conductor (electrolyte) The Metallic Conductor (electrical connection)

(1) The anode The anode corrodes by loss of electrons: M= Mz+ + ze

Anodic reaction Oxidation reaction Electron generation

(2) The cathode The cathode does not corrode. Most important cathodic reactions:

(i) pH < 7 2H+ + 2e- =H2 (ii) pH > = 7 2H2O + O2 + 4e- = 4OH-

Other cathodic reactions are possible Depending on the environment. Cathode

Cathodic reaction Reduction reaction Electron consumption

(3) An electrolyte (ionic conductor) a solution conducting electricity (4) Electrical connection the anode and cathode in a corrosion cell must be in electrical contact. Difference in free energies between the anode and the cathode produces electrical potential which is the driving force for corrosion reaction. Current: flow of electrons; Corrosion current: corrosion rate Points to note: all aqueous corrosion reactions can be thought of in terms of the simple corrosion cell. Separation of anode and cathode

permanent separation differential aeration random distribution [Back to Top]

4.3 Standard Electrode Potentials

The potential difference between the anode and cathode can be measured by voltage measuring device. The absolute potential of the anode and cathode cannot be measured directly. To define a standard electrode, all other potential measurements are made against the standard electrode. If the standard electrode potential is arbitrarily set to zero, the potential difference measured can be considered as the absolute potential.

Standard Hydrogen Electrode

The half-cell in which the hydrogen reaction takes place is called the standard hydrogen electrode, often abbreviated SHE

Standard Electrode Potential

The potential difference measured between metal, M, and the hydrogen electrode, under well defined conditions. Example: Iron corrodes in a solution of H+ (a) iron dissolves: half-cell reaction: Fe = Fe2+ + 2e(b) hydrogen gas formed: half-cell reaction: 2H+ + 2e- = H2 (c) overall reaction: corrosion reaction: Fe + 2H+ = Fe2+ + H2 Substituting into Nernst equation:

E=Eo - (0.059/2)lg{[Fe2+][H2]/[Fe][H+]2}
The terms [H+] and [H2] have been made to 1, [Fe] can be approximated as unity, so under standard conditions, [Fe2+] = 1 M,

E= Eo
The measured potential difference is the electrode potential of the iron under standard conditions. Points to note: if the measured potential is positive

dG=-zFE < 0, spontaneous reaction. Eo = + 0.44 V, dG is negative, iron corrodes spontaneously in acid. The standard electrode potential of other metals can be measured in the same way as for iron: Points to note

Standard reduction potential Standard redox potential

are used in stead of standard oxidation potential [Back to Top]

Summary
In this lecture, we introduced one of the most important equations in corrosion science and engineering, the Nernst Equation. We also analysed the four essential components of a corrosion cell, i.e., the ANODE, CATHODE, ELECTROLYTE and METALLIC (ELECTRON) CONDUCTOR. The Standard electrode potential of a metal in equilibrium condition is measured with reference to the Standard Hydrogen Electrode.

Lecture 4: The Theory for Aqueous Corrosion (II)

Reference Electrode Cell Potential Kinetics of Corrosion Reactions Summary Reading Assignments

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4.4 Reference Electrode

The standard hydrogen electrode is too complex for routine use in laboratory and field applications. Simpler reference electrodes: Saturated Calomel Electrode, SCE calomel, mercury chloride, Hg2Cl2

SCE

SHE

SCE is the most commonly used reference electrode in corrosion studies.Some common standard reference electrodes: refer to table in the textbook. [Back to Top]

4.5 Cell Potential

Dry batteries and Daniell cell Symbolism of a corrosion cell: Zn | Zn2+ || Cu2+ | Cu Zn electrode on the left, immersed in Zn2+ ions; Cu electrode on the right, immersed in Cu2+ ions. Ionic species are separated by || . Zinc is the anode, copper is the cathode. The two half-cell reactions are:

Zn = Zn2+ + 2eCu2+ + 2e- = Cu

The overall reaction Zn + Cu2+ = Zn2+ + Cu To find the theoretical cell potential, using Nernst equation for each of the half-cell reactions:

E(Zn/Zn2+)=Eo(Zn/Zn2+) - (0.059/2)lg[Zn2+], and E(Cu2+/Cu)=Eo(Cu2+/Cu) - (0.059/2)lg{1/[Cu2+]}. So the cell potential E(cell)=Eo(cell) - (0.059/2)lg{[Zn2+]/[Cu2+]} Convention:

do not use oxidation potential do use reduction potential

Eo(cell) = Eo(cathode) - Eo(anode) or Eo(cell) = Eo(right) - Eo(left)

Points to note: Current flow reduces potential A system will always react to oppose a change imposed upon it. Le Chatelier's principle The cell potential can be thought of as an ability to supply current. As soon as current is drawn, the ability is reduced. Thermodynamic can only indicate the tendency of a system to corrode, an equilibrium situation is required and this causes no net flow of current.

Corrosion reaction causes current to flow.

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4.6 Kinetics of Corrosion Reactions

Thermodynamics tells us about the tendency of a system to corrode NOT the rate of corrosion. The rate of a chemical or electrochemical reaction is dependent on the rate constant. The rate constant is related to the activation energy and the temperature of the system.

Exchange Current Density

For a metal M, in equilibrium with its own ions M = M+ + e, the rate of forward reaction (oxidation M=M++e) is exactly balanced by the rate of the reverse reaction (reduction M++e=M), i.e.

ia=ic=io

where i is the rate of reaction expressed in terms of current density and subscripts, a and c, represent the anodic (oxidation) and cathodic (reduction) processes. io is called the exchange current. It is to be noted that exchange current is always associated with an equilibrium condition, that is, the rate of forward (anodic) reaction equals that of the reverse (cathodic) reaction. The net current is zero.

Corrosion Rate and Faraday's Law of Electrolysis

The corrosion current density of a metal is related to the amount of mass reacted by Faraday's Law of electrolysis: i=zFJ, where J=(dM)/(dt), the flux of substance. [Back to Top]

Summary
In this lecture, we discussed some commonly used reference electrodes. The SCE electrode is most widely used in corrosion measurements. The cell potential can be obtained by subtracting the reduction potential of the anode from the reduction potential of the cathode. A positive cell potential indicates that reaction can take place naturally or spontaneously. The exchange current density is related to the equilibrium condition whereby no net current flows. Faraday's law of electrolysis relates the amount of mass reacted to the corrosion current density.

Lecture 5: The Theory for Aqueous Corrosion (III)

Polarisation Tafel Equation Corrosion Test Cell & Instrumentation Summary Reading Assignments

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4.7 Polarisation
When a metal is not in equilibrium with a solution of its ions, the electrode potential differs from the equilibrium potential by an amount known as the polarisation. Other terms having equivalent meaning are overvoltage and overpotential. The symbol commonly used for polarisation is . Polarisation is an extremely important corrosion parameter for which relationships have been established which enable useful statements to be made about the rates of corrosion processes.

In practical situations, polarisation is sometimes defined as the potential change away from some other arbitrary potential (often the mixed potential or the free corrosion potential, see section 4.9). Polarisation can also be expressed by E=E - Ecorr= [Back to Top] E.

Tafel Equation
Consider the process described in eqn. (4.38). In the last section we saw that corrosion rate and current density are directly related. At the beginning of this chapter we said that corrosion rate, v, could be expressed:

At equilibrium, the rate of the forward (anodic) reaction is ia, and equals the rate of the reverse (cathodic) reaction, ic. (Remember that io = ia = ic at equilibrium.) It is usually possible to treat the concentration of reactants (e.g. the solid metal, for the forward reaction) as constant, and we shall incorporate the term into a new constant, Ao. Thus, if we consider the rate of the forward reaction for which the activation free energy is shown , we can write eqn. (4.42) as:

When the forward reaction is faster than the reverse reaction (ia > ic) and an overall corrosion process occurs, equilibrium is destroyed and the free energies of the metal and its ions are at different levels, Fig. 4.6(a). The deviation from the equilibrium potential, the polarisation, is the combination of an anodic polarisation on the metal and a cathodic polarisation of the environment. (Compare Fig. 4.6(a) and (b): the energy of the metal has increased and that of the environment has decreased.) These potential deviations away from the equilibrium value may or may not be equal, and we shall assume for the moment that they are not. The changes are redrawn in Fig. 4.8.

If we define the total polarisation, then we can define the anodic polarisation and the cathodic polarisation. Note that in Fig. 4.8, the polarisations have been converted into free energies by multiplication by the factor, zF, as in the Faraday equation, (4.13). This enables us to determine the new activation energy for the anodic reaction, because the energy state of the metal has increased and the activation energy reduced. Thus we can write:

(Note that, similarly, the activation energy of cations, Mz+, being converted into M, i.e. the cathodic reaction, has increased. Substituting eqn. (4.43) into eqn. (4.45)

This equation is known as the Butler-Volmer equation and is much used in this subject. Now let

Converting to base 10 logarithms and rearranging eqn. (4.51)

the equation is known as the Tafel equation, whilst more specifically for the anode process:

The constants a and c, are called the anodic and cathodic beta or Tafel constants. Examination of the Tafel equation in its form of eqn. (4.55) tells us immediately that a graph for either of the two processes gives a straight line with a slope equal to the respective constant. The intercept, D, is shown. In the context of the Nernst equation (4.17) we found that 2.303RT/F has the value 0.059 and, suitably modified, sensible values for Tafel constants can readily be evaluated. As we have seen, z takes values 1, 2 or 3 and alpha is usually about 0.5. In practice, a value of +/- 0.03 to +/- 0.1 volts (or +/- 30 to +/- 100 mV) per decade of current density is common. [Back to Top]

4.11 Corrosion Test Cell & Instrumentation

The three-electrode cell is the standard laboratory apparatus for the quantitative investigation of the corrosion properties of materials. It is a refined version of the basic wet corrosion cell and a typical example is illustrated in Fig. 4.14. It can be used in many different types of corrosion experiments. First we shall examine the components in more detail. The working electrode is the name given to the electrode being investigated. It is useful, though not essential, if the electrode is designed to have a surface area of at least 100 square millimeters (1 cm2); current measurements can then be more readily converted into current densities, which should be used in calculations. Laboratory and field experiments are, however, often better performed using larger electrodes, if convenient. We use the term 'working electrode' rather than 'anode' because we are not limited to investigations of anodic behaviour alone: cathodic behaviour can also be examined. Practical working electrodes can be constructed in a variety of ways. A simple method is to mount a small specimen in cold-setting resin, Fig. 4.15(a). Electrical connection must be made to the specimen, and this can be done with solder or spot weld on the reverse side before mounting. After mounting, specimens are often ground and polished, as for metallographic examination. If this technique is used, the surface will be 'activated', in other words, passive films may have been either removed entirely or

just changed from the 'as-received' condition. This should always be borne in mind. Obviously, if the original passive film is part of the corrosion investigation, no pretreatment should be used. In fact, this is the biggest single reason for discrepancies between 'lab' and 'field' data. Surfaces in real engineering systems are most often 'asreceived' from manufacture and are not similar to specimens prepared for metallography. Although these specimen configurations are adequate for most purposes, accurate work may require a more carefully designed method of mounting. Two designs which are commercially available are illustrated in Fig. 4.15(b) and Fig. 4.15(c). Specimens in the form of thin discs of approximately 15 mm diameter, or cylinders of about 10 mm diameter x 10 mm length, can be quickly assembled into working electrodes with well-defined characteristics. The counter (auxiliary) electrode is the name given to the second electrode which is present specifically to carry the current in the circuit created by the investigation: it is not required for measurements of potential. Usually, a carbon rod is used, but it can be any material which will not introduce contaminating ions into the electrolyte. Platinum or gold can also be used with success, especially if space is at a premium, when smaller electrodes can be used; titanium is also suitable. The reference electrode is present to provide a very stable datum point against which the potential of the working electrode can be measured. It cannot itself carry any more than the most negligible current. If it did, it would participate in the cell reactions and its potential would no longer be constant, hence the requirement for the counter electrode. By far the most convenient reference electrode to use in such an experiment is a saturated calomel electrode, SCE. The external circuit can be varied considerably. The essential components are the following: A current measuring device. A potential measuring device. A source of potential. [Back to Top]

Summary
Polarisation is simply a shift or change in potential. In reality, many factors may cause polarisation of a system for better or for worse. Polarisation will affect the rate of corrosion reaction. Tafel Equation, undoubtedly, one of the most important equations in corrosion science and engineering, relates polarisation ( E or ) to the rate (ia or ic or icorr) of reactions. An experimental Tafel polarisation curve can be measured using a three-electrode corrosion cell interfaced with a potentiostat.

Lecture 6: The Theory for Aqueous Corrosion (IV)

Diffusion Processes Double Layer Mixed Potential Theory Summary Reading Assignments

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4.8 Diffusion Processes

The rate of a reaction is determined by the slowest step - rate determining step.

Activation controlled process

transport of reactants to the reaction site is relatively fast, activaton process (electron transfer) is the rate determining step.

Diffusion controlled process

transport of reactants is the rate determining step.

Diffusion Polarisation (Concentration Polarisation)

Take cathodic reduction of H+ as an example: 2H+ + 2e- = H2 At high reaction rates, cathodic reduction reactions deplete the adjacent solution of the dissolved species, H+ ions in this case. The concentration profile of H+ ions is shown schematically in the figure below.

Concentration profile of H+ in solution near the surface of an electrode (cathode). The process is controlled by diffusion or concentration polarisation. CB is the H+ concentration of the uniform bulk solution; Ce is the the H+ concentration at the electrode surface which is zero for a diffusion controlled process. is the thickness of the concentration gradient in solution (is also referred to as the Double Layer Thickness). Diffusion Limiting Current Density, iL, is a measure of the maximum reaction rate that can not be exceeded because of a limited diffusion rate of H+ in solution:

where DZ is the diffusivity of the reacting species, Z (H+) in this example. iL will be increased if

CB, bulk concentration increases T, temperature increases which increases

DZ. , decreases due to higher velocity/flow/solution agitation

The relationship between iL and concentration polarisation is:

For corrosion, concentration polarisation is primarily for cathodic processes, particularly, for the reduction of dissolved O2 in natural waters. Concentration polarisation for anodic oxidation during corrosion can usually be ignored because an unlimited supply of metal atoms is available at the metal/solution interface. However, when the rate of anodic reaction has become too high (during intentional anodic dissolution by impressed current such as electrochemical machining or electrorefining), concentration polarisation of the anodic reaction is possible as the rate-determining step is the the transport of oxidation products away from the

reaction site!
Combined Polarisation
Total cathodic polarisation is the sum of the activation and concentration polarisation:

For anodic process, concentration polarisation is usually absent, thus:

For detailed disscusion of concentration polarisation refer to the following book: "Principles and Prevention of Corrosion", Denny Jones, 2ed., Prentice-Hall, 1996, pp84-86 [Back to Top]

Double Layer
Double Layer: the non-homogeneous distribution of ions at the metal/solution interface. The double layer consists of two parts:

A compact layer, the Helmholtz layer, closest to the surface in which the distribution of charge, and hence potential, changes linearly with the distance from the electrode surface. A more diffuse outer layer, the Gouy-Chapman layer, in which the potential changes exponentially,

Fig4.7 The distribution of ions at the metal/solution interface and the variation of potential The following animation shows the process of ionization of metal immersed in water and the formation of the double layer.

[Back to Top]

4.9 Mixed Potential Theory

Single electrode (zinc in acid) reactions: Zn = Zn2+ + 2e- anodic reaction 2H+ + 2e- = H2 cathodic reaction Each has its own half-cell electrode potential and exchange current density. The two half-cell electrode potentials cannot coexist separately on the same electrically conductive surface (metal). Each must polarize or change potential to a common intermediate value, the mixture of the half-cell electrode potentials, most often called the mixed potential.

Other terms such as:

corrosion potential, Ecorr rest potential open circuit potential free corroding potential
all refer to the mixed potential of a corroding system. Two electrode system: examples: Zn-Fe

A mixed potential plot for the bimetallic couple of iron and zinc. The diagram also explains the higher corrosion rate of iron than zinc in hydrochloric acid solution. Despite the more positive reduction potential of iron, the evolution of hydrogen on iron has a high exchange current density. The principle of charge conservation applies to the corrosion reaction. In a corrosion reaction,

The total rate of oxidation must equal the total rate of reduction.
The sum of anodic oxidation currents must equal the sum of cathodic reduction currents. Evans diagram (Mixed Potential plot): schematic representation of the relationship between thermodynamics (potential) and kinetics (current) in a corrosion process. [Back to Top]

Summary
In this lecture, we discussed concentration polarisation, the formation of double layer at the metal/electrolyte interface and the mixed potential theory. Concentration polarisation is most often observed for the cathodic processes in a corroding system. When the availability of cathodic reactants at the cathode/electrolyte interface is limited, the rate of reaction will be determined by the rate of diffusion (iL). The double layer is an equilibrium arrangement of ions at the metal/solution interface and it has two parts - a compact fixed and a diffuse mobile layers. The mixed potential theory is based on the principle of charge conservation, i.e, the sum of anodic oxidation currents must equal the sum of cathodic reduction currents.

Lecture 7: Theory for Aqueous Corrosion (V)

Potential-pH Diagram Calculation & Construction Application and Limitation Summary Reading Assignments

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4.10 POTENTIAL-pH DIAGRAMS

Also called POURBAIX DIAGRAMS are charts based on thermodynamic calculations that can be used to distinguish a corroding condition from a non-corroding condition. CORRODING CONDITION: [Mn+] > 10-6 M IMMUNITY CONDITION: [Mn+] < 10-6 M Possible regions of a E-pH diagram: immunity,

corrosion or

passivation.
Each domain indicates a region in which one species is the most thermodynamically stable. If the metal is the most stable species then it is considered immune to corrosion, but if a soluble ion is most stable then the metal should corrode. A region in which an insoluble corrosion product is the most stable species is considered passive.

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Calculation and Construction of E-pH diagram

Identify all possible chemical and electrochemical reactions in the given system Apply Nernst equation to each possible reaction Make use of equilibrium constant if necessary Determine the relationship between between the potential (E) and the pH of the system Draw the potential as a function of pH in a chart [Mn+]=10-6 M is assumed as borderline for corrosion and non-corrosion region The chart is divided into different region representing different corroding conditions

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Application and Limitation

It is the E-pH diagram that made the study of corrosion a reputable science. Its applications include: Formulation of corrosion control methods (use of cathodic protection, anodic protection, corrosion inhibitors etc.) Identification of possible corroding states of the metal-H2O system (regions of immunity, passivation, corrosion or cracking) Prediction of most likely corrosion products (Fe2+ or Fe3+ ?) for the metal-H2O system Others

Practical limitations in the use of E-pH diagram are: E-pH diagram is based on thermodymanic calculations at assumed standard condition It is for pure metal in pure water system No kinetic information is given Effect of other ionic species such as Cl- is ignored Effect of flow or velocity on the stability of passivity is not taken into account

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Summary
E-pH diagram is a very useful chart that maps out the different regions of a corroding system. These possible regions are immunity,

corrosion, passivation

or cracking. It can be used to formulate corrosion control methods and to predict

the possible corrosion products. However, its practical application is limited by its lack of kinetic information and thermodynamic nature of origin.

Lecture 8: Dissimilar Metal Corrosion

EMF Series Galvanic Series Temperature Effect Area Effect Summary Reading Assignments

[Previous Lecture] [Next Lecture] [Course Outline] [General Info]

Dissimilar metal corrosion results from the coupling of two different metals. It is also called bimetallic corrosion or galvanic corrosion. The Electrochemical Motive Force (EMF) series
EMF series is an orderly listing of standard half-cell electrode potentials.

Galvanic Series
Galvanic series is an orderly list of corrosion potentials for various pure metals and alloys.

Comparison of EMF series and galvanic series

EMF Series absolute quantitative pure metals only half-cell potential standard conditions based on thermodynamic analysis used for theoretical calculations Point to note: Galvanic Series relative qualitative metals & alloys corrosion potential any specified conditions based on thermodynamic analysis used for practical applications

Sacrificial anode cathodic protection is the constructive use of the galvanic corrosion.
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Temperature Effect
The order of galvanic series may reverse under certain circumstances. e.g. Zn and Fe at elevated temperatures in some potable water systems The environment plays an important role in a corrosion process. [Back to Top]

Area Effect

Effects of coupling two dissimilar metals: The more active metal will become the anode of the couple in a wet corrosion cell. The more noble metal will become the cathode of the couple in a wet corrosion cell. The corrosion rate of the more active metal will be accelerated, while that of the more noble metal is retarded (the cathode may still corrode, depending upon the magnitude of the cathodic polarization induced by coupling of the more reactive metal). Cathode to anode area ratio:

Greater area ratio will result in a greater accelerating factor in the rate of galvanic corrosion
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Summary
Both EMF and Galvanic series are based on thermodynamic analysis of potentials. The potential difference between two dissimilar metals is the driving force for galvanic corrosion. Despite of being the first recorded form of corrosion some 200 years ago, Galvanic corrosion continues to be one of the most commonly encountered engineering problems. The coupling of dissimilar metals will accelerate the failure of the anodic member. The acceleration factor is affected by the cathode to anode area ratio. Changes in temperature may cause potential reversal.

Lecture 9: Selective Attack

What it is Intergranular Corrosion Prevention of Intergranular Corrosion Dealloying Summary Reading Assignments

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SELECTIVE ATTACK
Any corrosion which occurs at preferred site on a metal surface, for whatever reason, can be described as SELECTIVE ATTACK.

DEFECTS in metal crystal structures have electrochemical characteristics different from the rest. Most engineering metals contain VOLUME DEFEATS:

Voids Cracks Inclusions

To reveal the grain structure of a metal/alloy, polishing and etching of its sample are necessary. The etching process is an example of grain boundary corrosion. [Back to Top]

6.2 INTERGRANULAR CORROSION

INTERGRANULAR CORROSION occurs when a grain boundary area is preferentially attacked because of the presence of precipitates in these regions. Grain boundaries are preferred sites for:

Segregation Precipitation

Two types of segregates and precipitates: Intermetallics (intermediate constitutes): Formed from metal atoms having identifiable chemical formulae. Can either be anodic or cathodic to the metal. Compounds: Formed between metals and the nonmetallic elements, H, C, Si, N and O. Fe23C6 and MnS in steel are cathodic to ferrite.

Any metal in which intermetallics or compounds are present at grain boundaries will be susceptible to intergranular stress corrosion cracking. Austenitic stainless steels are most susceptible to intergranular corrosion. 18-8 or type 304 stainless steel: Fe18%Cr8%Ni When C% < 0.03%, only the austenite phase is stable. When C% > 0.03% austenite and ferrite mixed carbide (FeCr)23C6 are stable (Fig.6.2) The proportions of carbide obtained are dependent upon the rate of cooling: Fast cooling by water/oil quenching from > 1000oC suppresses carbide formation.

If the material is reheated within the range 600-850oC, carbide precipitation will occur at the grain boundaries. The material is thus said to be sensitized and is in a dangerous condition - susceptible to Intergranular corrosion cracking If the material is reheated below 600oC, the rate of diffusion of Cr is too slow for carbide precipitation to occur.

12%Cr + Fe === "stainless" steels precipitation of carbide (FeCr)23C6 causes Cr depletion (Cr<12%) in the metal adjacent to the precipitates. The steel is no longer "stainless". Cr depleted zone is very anodic to the rest of the grains. Severe attack occurs adjacent to the grain boundary. Whole grains may become detached from the material Sensitisation may occur during:

manufacturing welding operating

If Cr carbide nuclei pre-exist in grain boundary regions, sensitisation can occur at temperatures in the range 300-320oC. Weld decay === Sensitisation caused by welding. Use stainless steels with caution !!! [Back to Top]

Methods of prevention
Lower the C content to below 0.03%, so that the carbides are not stable. Add alloying elements that are strong carbide formers (e.g. Ti and Nb are preferentially combined with C, no Cr is consumed). %Ti/Nb = 5/10 x %C : stabilized steel Use high temperature solution heat treatment to dissolve the precipitates. (post weld heat treatment of sensitized steel).

Case 6.1

While attempting to fold the tail pylon of a helicopter it was found that it was not possible to disengage the locking assembly because of a fractured , unstabilised stainless steel pin (Fig.6.3a). Examination showed that the most likely cause of failure was intergranular cracking (Fig.6.3b) initiated by a network of grain boundary precipitates (Fig.6.3c) [Back to Top]

6.3 Dealloying
The net removal of one element from an alloy is often referred to as dealloying. Uniform removal does not alter the overall geometry Dealloying leaves a porous material with reduced or no mechanical strength. Classical problem: dezincification loss of zinc from brass: dezincification loss of nickel from copper alloys: denickelification loss of Al from copper alloys: dealuminification loss of tin from copper alloys: destannification

Two groups of brass:

70/30 single phase 60/40 two-phase

Prevention of dezincification by addition of arsenic to brass: 70/30 brass + arsenic =Admiralty brass = inhibited brass uninhibited brass should never be specified for uses involving immersion in either fresh or sea water. Case 6.2 The component is a 60/40 brass casting used as a connector in a water supply. The dark inner areas are dezincified and the left hand region has fractured because of the embrittlement caused by the extreme porosity. Case 6.3 The component is part of a cast aluminum bronze sea water valve which had originally suffered wastage because of erosion, but which had not dealloyed. The component was recovered by depositing 60/40 brass along the shank and around the

closing surface. The reclaimed areas have suffered dezincification and some has been broken off. Case 6.4 Fig.6.5 shows a leaded brass bolt, 12 mm in diameter, which suffered dezincification to a depth of 3 mm in several years exposure to sea water. The fractures are a direct result of the embrittlement of the material. 60/40 Brass contains a and b phases. %Zn in a phase < %Zn in b phase. ECorr a = -230 mV, cathodic ECorr b = -285 mV, anodic b phase in brass would be attacked first: Zn in b phase is dissolved quickly, Cu is much less affected. [Back to Top]

Summary
Selective attack is caused by metallurgical factor of the material rather than chemistry factor of the environment. Segregations and precipitations along grain boundaries create preferential paths for the anodic and cathodic reactions. Dealloying is also caused by the metallurgical factor in that the alloying elements have wide differing electrochemical potential. The anodic constituent will be preferentially leached out of the alloy, leaving behind a porous material with no strength.

Lecture 10: Crevice Corrosion and Pitting

The Nature of Metal/Environment Crevice Corrosion Mechanism of Crevice Corrosion Pitting Corrosion Characteristics of Pitting Mechanism of Pitting Differential Aeration Summary Reading Assignments

[Previous Lecture] [Next Lecture] [Course Outline] [General Info] [Study Guide]

The Nature of Metal/Environment

uniform composition of alloy + uniform composition of environment => uniform corrosion non-uniform composition of alloy + uniform composition of environment => Galvanic corrosion/Intergranular corrosion non-uniform composition of alloy + non-uniform composition of environment=> localised corrosion: crevice/pitting Most of practical situations are non-uniform.

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Crevice corrosion:
Localised corrosion resulting from the formation of a concentration cell in a crevice formed between a metal and nonmetal, or between two metal surfaces. Two prerequisites:

a physical crevice between two surfaces the formation of concentration cell

In 1981, it was reported that one of the most serious problems in the US nuclear industry was "denting" (localised attack) of Inconel 600 tubing because of the corrosion in crevices between the tubes and carbon steel support plates. With about 60 steam generators affected, the COST of rectifying the known problems was estimated to be US$6000 million.
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The Mechanisms of Crevice Corrosion

The Fontana and Greene Model Stage 1 corrosion occurs as normal both inside and outside the crevice: anodic reaction: M=>Mn+ + ne cathodic reaction: O2+2H2O +4e=4OH-

The positively charged metallic ions are electrostatically counterbalanced by OHStage 2 at this stage, the cathodic reaction inside the crevice consumed most of the oxygen available. Inside the Crevice O2 depleted Anodic reaction Stage 3 Inside the Crevice O2 depleted Anodic reaction High [Mn+] concentration Overall positive High [Cl-] concentration Outside the Crevice O2 readily available cathodic reaction High [OH ] concentration Overall negative Normal [Cl-] concentration
-

Outside the Crevice O2 readily available cathodic reaction

Cl- and OH- diffuse into the crevice to maintain a minimum potential energy. =>Metal chloride is formed. Hydrolysis of metal chloride lowers pH=> MCln + nH2O = M(OH)n + nHCl Stage 4 Inside the Crevice Low pH High [Cl-] concentration High [Mn+] concentration Outside the Crevice Normal pH Normal [Cl-] concentration Low [Mn+] concentration

More Mn+ ions attrack more Cl- leads to lower pH inside crevice => accelerate metal dissolution=>More Mn+ ions produced =>attrack more

Cl- =>lower pH

=> autocatalytic process

For stainless steel, it is the dissolution and hydrolysis of Cr that leads to the fall in pH: Cr3+ + 3H2O = Cr(OH)3 + 3H+
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PITTING CORROSION
Definition: Extremely localised attack that results in holes in metals.

Characteristics of pitting:
(1) difficult to detect small in size covered by corr products undercut surfaces, damage to sub-surfaces are severe. initiation/incubation period uncertain

(2) difficult to measure/compare

depth of penetration varies number of pits varies

(3) difficult to predict

requires long time to initiate

(4) vicious

highly localised intense attack equipment fails with extreme suddenness

(5) shape of pits sharply defined holes, no attack on most metal surface.

rough surface, pits close together line in direction of gravity

(6) growth of pits requires 0.5-1 year to initiate once started penetrate metal fast undercut surfaces, sub-surface damage severe.

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Mechanism of pitting
Propagation mechanism same as crevice corrosion: concentration cell causes local acidification within pit. autocatalytic nature Initiation of pitting is different from crevice: Crevice requires physical crevice - a gap between two surfaces Pitting has no geometrical requirement
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Differential Aeration Caused Pitting

Pitting underneath a water droplet (a) initiation period: general/uniform corrosion Fe = Fe2+ + 2e (b) the center of the water droplet is depleted in O2. Concentration cell causes separation of anode and cathode: centre of droplet: anode edge of droplet: cathode

[Back to Top]

Summary
Pitting corrosion is one of the most damaging forms of corrosion. It may be initiated by metallurgical factor or environmental factor or both. Once initiated, the propagation is autocatalytic (self-accelerating) in nature. Crevice corrosion is caused by the presence of a physical gap (crevice) between two surfaces that leads to the set up of differential aeration cell. Inside the crevice, anodic reaction is also selfaccelerating (autocatalytic) in nature. The processes inside the crevice is essentially the same as the propagation of pitting. Stainless steels and alloys are particularly susceptible to pitting and crevice corrosion.

Lecture 11: Electrochemical Techniques

Polarisation Curves of Passive Metal Unstable Passivation Cyclic Pitting Scan and Pitting Potential Applications of Electrochemical Techniques Summary Reading Assignments

[Previous Lecture] [Next Lecture] [Course Outline] [General Info] [Study Guide]

Polarisation Curves of Passivating Metals

From previous lectures and tutorials we have observed that for some metals/alloys, when polarisation (anodic) increases, the current density and hence the corrosion rate of the metal/alloy increases; while for others, the corrosion rate will drastically decrease to a stable value and become independent of the polarisation applied. This behavior is referred to as passivating behavior and the metal/environment is referred to as a passivating system. Polarisation curves are particularly valuable in quantifying the behaviour of materials under various conditions. This section explains how electrochemical techniques are used to assess materials resistance to corrosion and what information can be obtained.

The schematic potentiodynamic polarisation behaviour of passivating metals. (a) General polarisation plot showing three possible theoretical cathode processes. The solid line in Fig. 7.6(a) is a schematic E/lg i plot for a metal in a mild environment, such as an austenitic stainless steel in dilute sulphuric acid. AB represents cathodic behaviour, BG is the active zone. The metal is not passivated at its free corrosion potential, B. AC and DC are Tafel-type straight lines drawn for the reduction and oxidation reactions of the normal metal dissolution (M=M++e). At potentials more positive than B, corrosion rate increases, and reaches a maximum at the passivation potential, G, which is often given the symbol, Epp. The transition from active dissolution occurs as a solid species becomes more thermodynamically stable than the metal ion. A protective film begins to form and causes a sudden drop in corrosion current density in the region G to J. From J to P, the passive zone, the current density is maintained at a steady, low level, until, at P, breakdown of the protective film begins. It is here that the likelihood of pitting is greatest, and consequently the potential Ec, often called the critical pitting or breakdown potential. It is a useful parameter in assessing pitting properties of materials. It should be noted that it is not an absolute parameter, and varies according to both metallurgical and environmental conditions.

At potentials more positive than P, the current density begins to rise as more and more pits propagate.

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Unstable Passivation
Some passivating metals have E/lg i plots which may show more than one corrosion potentials like in Fig.7.6(b). This indicates an unstable passivating system.

Fig.7.6(b) The schematic potentiodynamic polarisation behaviour of passivating metals. These differences are caused by variation in the dominant cathodic process. Three possibilities are shown as dashed lines, CA, KF, and LN in Fig. 7.6(a). A different type of polarisation plot will be measured, depending upon which cathodic process predominates.

There are three usual cathodic processes: hydrogen evolution, oxygen reduction and

metal cation reduction. The experimental plot is always the sum of all anodic and cathodic currents.

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Cyclic Pitting Scan and Pitting Potential

Fig.7.8(a) A cyclic polarisation (pitting 'hysteresis') curve for type 304 stainless steel in aerated seawater at 25 oC, scan rate: 0.1 mV s-1. The broken line shows a similar plot using aerated seawater + 4.5 M sodium chloride and HCl, adjusted to pH 1.2. Ec is the critical pitting potential above which new pits will initiate and existing pits will propagate Ep is the protection potential below which there is no pitting Ep<E<Ec between the two, existing pits will propagate but no new pits will form

In general, the larger the area of the hysteresis loop, the greater the susceptibility to pitting corrosion. [Back to Top]

Applications of Electrochemical Techniques

Electrochemical techniques can be used to ASSESS materials resistance to

general corrosion crevice corrosion pitting corrosion intergranular cracking

HOW ??? Potentiodynamic polarisation measurement: the E-lgi plot for information on

pitting potential critical pitting potential protection potential breakdown potential critical pitting temperature active region passive region transpassive region [Back to Top]

Summary
A corroding system can be classified as passive or non-passive system depending on the behaviour under anodic polarisation. Polarisation curves for the passive systems may show active/passive and/or passive/transpassive transitions. The current density in the passive state is generally very low compared with that in the active state. The stability of passivation depends on the predominant cathodic process (hydrogen evolution, reduction oxygen and reduction metal ions). Electrochemical techniques provide rapid, accurate and quantitative evaluation of a materials resistance to corrosion, particularly pitting. The critical pitting potential and the protection potential can be obtained from a cyclic pitting scan.

Lecture 12: Erosion Corrosion and Environment - Sensitive Cracking

Erosion Corrosion Effect of Flow Rate Impingement Attack Cavitation Damage Environment-Sensitive Cracking Mechanism Prevention Summary Reading Assignments

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Erosion Corrosion
The progressive loss of material from a solid surface due to mechanical interaction between that surface and a fluid.
8.1. EFFECT OF FLOW RATE
(1) disturbs equilibrium, increases dissolution; (2) supplies oxygen, minimizes differential aeration cells. (3) supplies aggressive ions, increases dosage of additives (inhibitors etc). (4) carries solid particles, scours away protective layers, enhances corrosion. (5) sufficient flow to prevent deposition of dirt, minimizes differential-aeration cells.

The effects of flow rate are unpredictable !!!

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IMPINGEMENT ATTACK
Localized erosion corrosion caused by turbulence or impinging flow at certain points. Examples: a sudden change in the bore diameter or direction of a pipe; a badly fitting gasket or joint which introduces a discontinuity in the otherwise smooth metal surface; a crevice which allows liquid flow outside the main body of fluid; presence of deposit which may disturb the laminar flow.

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8.2 CAVITATION DAMAGE

A particular form of erosion corrosion caused by the formation and collapse of bubbles of vapor on metal surfaces. In cavitation components moving at high speed through a stationary fluid such as propellers, impellers, hydraulic turbine gear. In erosion corrosion fluid flows across stationary metal surfaces such as pipes, tanks

[Back to Top]

Environment-Sensitive Cracking
Season cracking (1921): cracking of brass cartridges in the monsoon season residual stress from manufacturing process + ammonia from horse urine => cracking of brass stress corrosion cracking, environment-sensitive, caustic embrittlement => explosion of boilers mild steel + deposit of caustics (NaOH added to boiler water to prevent scaling) Fig10.2 A particular metal/environment in the presence of tensile stress => environmentsensitive cracking

Mechanisms
Pre-existing active paths model. e.g.sensitized stainless steel, intergranular SCC Strain-generated active paths model. e.g. for passive metals stress ruptures film locally setting up active-passive cell Adsorption-related mechanism damaging species adsorbs on the crack surfaces, lowering the fracture stress

Prevention of SCC
Select a material not known to crack in the specific env involved; ensure that the microstructure is not susceptible to intergranular corrosion cracking. Lower internal stresses on the metal and use stress relief anneal Design to minimize tensile stresses and stress raisers.Eliminate the specific species (Cl-, NH3, etc) from the environment.

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Summary
In erosion corrosion , cavitation and impingement, the mechanical factor (flow rate) plays a more important role than the electrochemical processes. In environment-sensitive cracking, three essential factors (tensile stress,

specific chemical species and a susceptible material) are combined to cause a cracking.

Lecture 13: Basic Principles of Corrosion Control

Basic Principles Materials Selection Design Against Corrosion Atmospheric Corrosion Corrosion Inhibitors Summary Reading Assignments

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Basic Principles of Corrosion Control

(1) Materials selection (2) Design (3) Coatings (4) Inhibitors (5) Electrochemical protection [Back to Top]

Materials Selection
The minimum cost materials of low corrosion resistance require frequent maintenance and replacement.

Design Against Corrosion

Process Variables: Relative humidity Temperature Pressure pH

O2 concentration Solid or dissolved pollutants Concentration Velocity Stress etc

These variables have obvious effects on corrosion rate and materials of construction. e.g. when ToC is up , corrosion rate goes up , require more resistant materials.

Corrosion protection measures:

do not introduce localized galvanic cells into the system. use of coatings, paintings and electrochemical protection.

Corrosion data: obtained under specific conditions must be treated with care when used

Design against corrosion:

(1) avoid bimetallic corrosion cell (2) avoid differential aeration cells: crevices, debris traps (3) avoid turbulent flow [Back to Top]

Atmospheric Corrosion
Major factors affecting atmospheric corrosion: (1) Dust content suspended salt particles, carbon compounds and metal oxides, etc. => abrasive and corrosive actions: combined with moisture initiate corrosion by galvanic or differential aeration. (2) Gases in the atmosphere

SO2, SO3 and H2S from burning of coal, oil and gasoline produce acids, increases corrosion rate. (3) Moisture (humidity) high R.H. results in differential aeration cells (4) temperature when ToC is up, corrosion rate is up; but dissolved gases decreases , so corrosion rate decreases . [Back to Top]

Corrosion Control by Inhibitors

Inhibitor: a chemical when added in small quantity to the environ reduces corrosion
rate. Classification: (1) anodic inhibitors/passivators: retard the anodic process, e.g. molybdates, silicates, phosphates, borates (requires dissolved O2) chromates, nitrates (self-oxidizing)

(2) cathodic inhibitors: retard the cathodic process, e.g: zinc salts, magnesium salts (3) mixed/adsorption inhibitors: retard both anodic and cathodic processes, e.g: chromate/polyphosphate/zinc Anodic inhibitor more efficient but dangerous; Cathodic inhibitor safer to use but less efficient; Mixed inhibitor efficient and safe Cathodic type to retard the overall corr rate Anodic type to seal off the active anodic sites. [Back to Top]

Summary
It is easier to erase lines in a drawing than to replace failed components in a plant. Materials selection and design are most effective and economical ways of corrosion control and prevention. Relative humidity is a most important factor in atmospheric corrosion. The effect of temperature is

somehow unpredictable. Coatings and electrochemical protection can also be specified at the design stage. Corrosion inhibitors if used properly can reduce the corrosion rate by 90% or more but they may induce localised corrosion such as pitting.

Lecture 14 : Corrosion Control by Barrier Coatings

Function and Classification Paints, Composition and Failure Metallic Coatings: Properties Metallic Coating Methods Corrosion Behavior of Metallic Coatings Summary Reading Assignments

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Function and Classification

(1) to separate the metal/environment (2) to control the micro-environment

Classification of Coatings:
(1) metallic

anodic cathodic

(2) non-metallic (paints)

Composition of paint
(1) a vehicle: controls the paint fluidity, drying (2) a pigment: controls corr rxn or diffusion (3) additives: accelerate the drying process

Paint Failure
(1) poor or inadequate surface preparation: surface rust, surface too rough

(2) applied under unsuitable condition or by inappropriate methods relative humidity too high temperature variations [Back to Top]

Metallic Coatings
ideal properties: (1) more resist to attack (2) do not accelerate local corr at defects (3) good physical properties elasticity, hardness (4) compatible with fabrication of the complete components (5) uniform thickness, pore free [Back to Top]

Metallic Coating Methods

(1) electroplating to be plated => cathode plating metal => anode (2) hot dipping object dipped into a bath of molten coating metal => good bonding due to interfacial alloying hot dipping in zinc/aluminium => galvanizing fig 12.6, 12.7, 14.7 (3) spray coats melted metal is sprayed on substrate surface; more porous than (1) & (2) (4) clad coatingss corr resistant skins applied by rolling (high pressure), explosive welding for building up a welded coat

(5) diffusion coatings limited to small objects [Back to Top]

The Corrosion Behavior of Metallic Coatings

factors: (1) nature of electrolyte (ph, toc) (2) O2 concentration (3) cathode/anode area ratio (4) nature of coat/substrate

Zinc coating
anodic to steel substrate service life depends on thickness

Aluminium
in Cl environment, anodic to steel in others, may be cathodic to steel

Nickel and chromium

all cathodic to steel; barrier coat

Tin coating
used for cans in food industry inside anodic to steel (organic acids) outside cathodic to steel [Back to Top]

Summary
Coatings either metallic or non-metallic in nature serves as a physical barrier between the metal substrate and its environment. Anodic (metallic) coatings such as zinc on steel can also provide sacrificial protection. Cathodic (metallic) coatings may induce or accelerate localised attack on the substrate

Lecture 15: Cathodic Protection

Theoretical Basis Cathodic Protection Potential Sacrificial Anode Cathodic Protection Summary Reading Assignments

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Theoretical Basis
Metal to be protected is made the cathode (1) by coupling a more reactive metal sacrificial anode (2) applying an external current (impressed current) E-pH diagram can be used to formulate ways to protect iron: (a) increase pH of the environment so that Fe is shifted into the passivation region (b) potential is made more negative so that Fe is shifted into the immunity region E < -800 mv (CSE) copper-copper sulphate electrode (c) potential is made more positive so that Fe is shifted into the passive region (formation of insoluble corrosion products

Cathodic Protection Potential

Empirical potential range for steel : -800 mV/-900 mV CSE Typically: -850 mV CSE Applied potential causes polarisation; polarisation affects corrosion rate.

Cathodic polarisation always suppresses rate of anodic reaction (rate of metal dissolution or corrosion)

Sacrificial Anode Cathodic Protection

Common sacrificial anodes

zinc magnesium aluminium

are used to protect

buried pipelines offshore structures ship's hull

Combined use of cathodic protection with paints is ideal for steel structure as (1) defects in paints will be cathodically protected against corrosion (2) most surface area is painted thus the required cathodic protection current is small [Back to Top]

Summary
Cathodic protection is the only method that can reduce the corrosion rate to zero (in theory). In practice, a polarisation of 200 mV below the corrosion potential for steel structures is all that needed to reduce the corrosion rate to a negligible level. This cathodic polarisation can be achieved by the use of sacrificial anodes or impressed current..

Lecture 16: ICCP and Anodic Protection

ICCP Principle and Applications

Anodic Protection Comparison of Protection: Cathodic or Anodic? Summary Reading Assignments

[Previous Lecture] [Course Outline] [General Info] [Study Guide]

ICCP Principle and Application

In Impressed Current Cathodic Protection, electrons from an external DC power source are pumped into the steel structure and cathodically polarise it by typically 200 mV below the corrosion potential (like the case in sacrificial anode cathodic protection). ICCP can be used to protect

buried pipelines offshore structures ship's hull

Combined use of cathodic protection with paints is ideal for steel structure as (1) defects in paints will be cathodically protected against corrosion (2) most surface area is painted thus the required cathodic protection current is small

Anodic Protection
In anodic protection, the metal to be protected is made the anode corrosion products protective active-passive metals/alloys

Cathodic Protection or Anodic Protection? -The Comparison Cathodic Protection Advantages

Anodic Protection

can be used

can be used in

for all metals installation cost is low corrosion rate can be reduced to zero

extremely aggressive environment applied current is direct measure of corr rate operating conditions can be easily controlled

operation cost low

Limitations

can only be used in weak to moderate environment

only applicable to active-passive metals

operating conditions must be determined by empirical testing.

installation cost is

high

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Summary
ICCP cathodic protection differs from sacrificial anode cathodic protection in that an external current is applied from a power source. In anodic protection, the metal to be protected is made the anode by making the potential more positive (above the corrosion potential).