Corrosion Mechanisms

Randhir Kumar Singh Asst Professor OPJIT

Chemical vs. Electrochemical Reactions

Chemical reactions are those in which elements are added or removed from a chemical species.

Electrochemical reactions are chemical reactions in which not only elements may be added or removed from a chemical species but at least one of the species undergoes a change in the number of valence electron. Corrosion processes are electrochemical in nature.
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Simplest Example: Dry Cell Battery

Faradays laws of electrolysis, in chemistry, quantitative laws used to express magnitudes of electrolytic effects, first described by the English scientist Michael Faraday in 1833.

The laws state that (1) the amount of chemical change produced by current at an electrode-electrolyte boundary is proportional to the quantity of electricity used, and (2) the amounts of chemical changes produced by the same quantity of electricity in different substances are proportional to their equivalent weights.

Contd
In electrolytic reactions, the equivalent weight of a substance is the gram formula weight associated with a unit gain or loss of electron. The quantity of electricity that will cause a chemical change of one equivalent weight unit has been designated a faraday. It is equivalent to 9.6485309 104 coulombs of electricity.

Thus, in the electrolysis of fused magnesium chloride, MgCl2, one faraday of electricity will deposit 24.312/2 grams of magnesium at the negative electrode and liberate 35.453 grams of chlorine at the positive electrode.
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Faradays Law

The mass of an element discharged at an electrode is directly proportional to the amount of electrical charge passed through the electrode weight of metal reacting = kIt
where I = Current Intensity t = time of current passage k = Constant
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What Happens if the Battery is Not in Use?

There will be some local action current generated by local action cells because of other metallic impurities in zinc

Shelf life of an ordinary zinc-carbon rod battery is limited

Local Action Cell

Anode & Cathode

Anode

Loss of electron in oxidation Oxidation always occurs at the anode

Cathode

Gain of electron in reduction Reduction always occurs at the cathode

Difference between Electrochemical and Electrolytic Cell

fes/fe2+aq //sn2+aq/sns Both types of cells consist of two electrodes connected to an electrolyte (an ionically conducting phase). Electrode reactions then take place at the electrode-solution surfaces. The change from electronic current to ionic current and visa versa are always accompanied by oxidation/reduction reactions. An electrochemical cell is simply a device that converts chemical energy into electrical energy when a chemical reaction is occurring in a cell. An electrolytic cell converts electrical energy into chemical energy. In an electrochemical cell the reaction occurs spontaneously at the electrodes, while an electrolytic cell reaction is not spontaneous at the electrodes - the reaction has to be forced by applying an external electrical current.

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In an electrochemical cell the cathode is positive and the anode is negative. In an electrolytic cell the cathode is negative and the anode is positive (does this mean that the electrons are going against their gradient here?). In a spontaneous chemical reaction electrons are passed directly from one element to another. In an electrochemical cell these simultaneous redox reactions are "spatially separated" - i.e. happen at different places. The resultant ions then combine to form a new product. During this process electrons are conducted from the anode to the cathode through an outside electrical current which can be used. This action can be reversed in a electrolytic cell. Electrochemical cells are used usually as batteries, while electrolytic cells are used for electroplating metals. Also, the recharging of a rechargeable battery is an electrolytic reaction.

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Corrosion Cells

Galvanic cell (Dissimilar electrode cell) dissimilar metals Salt concentration cell difference in composition of aqueous environment Differential aeration cell difference in oxygen concentration

Differential temperature cell difference in temperature distribution over the body of the metallic material
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Dissimilar Electrode Cell

When a cell is produced due to two dissimilar metals it is called dissimilar electrode cell

Dry cell Zn anode Local action cell A brass fitting connected to a steel pipe A bronze propeller in contact with the steel hull of a ship

Cu cathode HCl Solution

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Salt Concentration Cell

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Differential Aeration Cell

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Corrosion at the bottom of the electrical poles

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Differential Temperature Cell

This is the type of cell form when two identical electrodes are immersed in same electrolyte, but the electrodes are immersed into solution of two different temperatures
This type of cell formation takes place in the heat exchanger equipment where temperature difference exists at the same metal component exposed to same environment For example for CuSO4 electrolyte & Cu electrode the electrode in contact with hot solution acts as cathode.
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Factors affecting choice of an engineering material

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Factors affecting corrosion resistance of a metal

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Corrosion Rate Expressions

mm/y gmd ipy mpy

mcd

millimeters penetration per year grams per square meter per day inches penetration per year mils penetration per year (1000 mil = 1 inch) milligrams per square centimeter per day

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Corrosion Rate Expressions

The most used expression for Corrosion Rate in the US is the mpy (Mils per year). Mils per year (mpy) = 534W/DAT To convert corrosion rate (corrosion rate conversion) between the mpy and the equivalent in metric unit mm/y (millimeter per year): 1 mpy = 0.0254 mm/y = 25.4 micron/y To calculate the corrosion rate from metal loss:

mm /y = 87.6 x (W / DAT)

W = weight loss in mg D = density of specimen material in g/cm 3 A = area in cm2 T= exposure time in hours
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Classification of metallic materials according to their rate of uniform attack

A. <0.005 ipy (<0.15 mm/y) Metals in this category have good corrosion resistance and can be used for critical parts B. 0.005 to 0.05 ipy (0.15 mm/y to 1.5 mm/y) Metals in this group are satisfactory if a higher rate of corrosion can be tolerated C. >0.05 ipy (>1.5 mm/y) Usually not satisfactory

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Electrochemical Aspects
Electrochemical Reactions

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Electrochemical Reactions

The above concept is illustrated in the Fig.1

Fig.1 Electrochemical reactions occurring during corrosion of zinc in air-free hydrochloric acid
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Electrochemical Reactions

Fig.2 Electrochemical reactions occurring during corrosion of zinc in aerated hydrochloric acid

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Let us look at a Zn-H Cell

The Zn electrode moves away from equilibrium by the removal of negative charges from the Zn plate and positive ions are released from the Zn plate to the liquid (a) Zn is dissolved at the same rate as electrons are transported to the Pt plate, where they are consumed in the hydrogen reaction The same cell process can be totally obtained on a Zn plate submerged in a solution containing hydrogen ions and Zn ions (b) The reactions are accompanied by the same changes in free enthalpy and have the same equilibrium potentials as before However, there is a higher resistance against the hydrogen reaction on the Zn plate than on Pt, and thus the reaction rate will be lower on the Zn surface

(a)

(b)

So We Also Need to Know

Electrode kinetics to predict the corrosion rates for the actual conditions

Single and mixed electrodes

Whenever only one electrode reaction takes place on a metal surface in a given solution, that system is called a single electrode. This is the case for copper immersed into de-aerated and slightly acidic copper sulfate solution: Cu2+ + 2 e = Cu -- (1) The open circuit potential (ocp) is the potential set up spontaneously by an electrode in the absence of an external current. For a single electrode, the open circuit potential is equal to the equilibrium potential, Erev.

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Single and mixed electrodes

Most often, several electrode reactions take place simultaneously at a metal electrolyte interface. Such systems are referred to as mixed electrodes. If, in the previous example, the copper sulfate solution is aerated, two electrode reactions (called partial reactions) are observed at the open circuit potential; the oxidation of copper CuCu2+ + 2 e -- (2) and the reduction of oxygen: O2 + 2H+ + 2 e H2O -- (3) The corresponding overall reaction is Cu + O2 + 2H+ Cu 2+ H2O -- (4) The copper thus corrodes without any external current. The open circuit potential of a mixed electrode undergoing corrosion, is called the corrosion potential (in the literature it is sometimes also called the free corrosion potential). The corrosion potential has a value that lies in between the equilibrium potentials of the partial electrode reactions. In contrast to the equilibrium potential, which is a thermodynamic quantity, the corrosion potential is determined by kinetics; its value depends on the rates of both the anodic and the cathodic partial reactions present.

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Single and mixed electrodes

Figure A copper electrode in contact with itw own ions (single electrode) and with an aerated solution (mixed electrode).
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Polarization and Overpotential

Polarization

Electrode reactions are assumed to induce deviations from equilibrium due to the passage of an electrical current through an electrochemical cell causing a change in the electrode potential. This electrochemical phenomenon is referred to as polarization. The polarization expresses the difference between the potential of a mixed electrode subjected to anodic or cathodic polarization and its corrosion potential. = E Ecor A polarization of > 0 indicates an anodic and a polarization of < 0 a cathodic current flow

Overpotential The deviation from equilibrium causes an electrical potential difference between the polarized and the equilibrium (unpolarized) electrode potential known as overpotential = E Erev A positive overpotential indicates that an anodic current is crossing the interface; a negative one means that the current is cathodic.

Polarization and Overpotential

Equilibrium potential for cathodic reaction = E oc

Equilibrium potential for anodic reaction = E oa Real potential = E

Cathodic Overpotential c = E Eoc < 0 anodic Overpotential a = E Eoa > 0

The Polarized Cell

Exchange Current Density

At the equilibrium potential of a reaction, a reduction and an oxidation reaction occur, both at the same rate. For example, on the Zn electrode, Zn ions are released from the metal and discharged on the metal at the same rate The reaction rate in each direction can also be expressed by the transport rate of electric charges, i.e. by current or current density, called, respectively, exchange current, Io, and (more frequently used) exchange current density, io. The net reaction rate and net current density are zero

How Polarization is Measured

Causes of Polarization

Depending on the type of resistance that limits the reaction rate, we are talking about three different kinds of polarization

activation polarization concentration polarization and resistance (ohmic) polarization or IR Drop

Activation Polarization

When current flows through the anode and the cathode electrodes, their shift in potential is partly because of activation polarization An electrochemical process that is controlled by reaction sequence at the metal-electrolyte interface. This is easily illustrated by considering hydrogen evolution reaction on zinc during corrosion in acid solution. An electrochemical reaction may consist of several steps The slowest step determines the rate of the reaction which requires activation energy to proceed Subsequent shift in potential or polarization is termed activation polarization Activation polarization usually is the controlling factor during corrosion in media containing a high concentration of active species(e.g. concentrated acids). Most important example is that of hydrogen ion reduction at a cathode, H+ + e- H2, the polarization is termed as hydrogen overpotential

Activation Polarization

Fig. Hydrogen-reduction reaction under activation control(simplified).

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Hydrogen Overpotential

Hydrogen evaluation at a platinum electrode:

H+ + e- Hads 2Hads H2

Step 2 is rate limiting step and its rate determines the value of hydrogen overpotential on platinum

Tafel Equation

Activation polarization () increases with current density in accord with Tafel equation: i log io

The Tafel constant is given by:

2.3RT nF

Overpotential Values

Concentration Polarization

It refers to electrochemical reactions that are controlled by the diffusion in electrolyte. Sometimes the mass transport within the solution may be rate determining in such cases we have concentration polarization Concentration polarization implies either there is a shortage of reactants at the electrode or that an accumulation of reaction product occurs Concentration polarization generally predominates when the concentration of the reducible species is small(e.g. dilute acids, aerated salt solutions).

Concentration Polarization

Fig.3 Concentration polarization during hydrogen reduction.

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Concentration Polarization: reduction of O 4H 4e 2H 2O oxygen 2

il k

IR Drop

When polarization is measured with a potentiometer and a reference electrode-Luggin probe combination, the measured potential includes the potential drop due to the electrolyte resistance and possible film formation on the electrode surface The drop in potential between the electrode and the tip of Luggin probe equals iR.

If l is the length of the electrode path of cross sectional area s, k is the specific conductivity, and i is the current density then resistance l R k il iR drop in volts = k

Combined Polarization

Total polarization of an electrode is the sum of the individual contributions,

T a c r

If neglect IR drop or resistance polarization is neglected then:

T a c

Combined Polarization

Effect of temperature, concentration and velocity of the aqueous environment on combined polarization is shown in the figure

Passivity

Passivity refers to the loss of chemical reactivity experienced by certain metals and alloys under particular environmental conditions.

Fig. Corrosion rate of a metal as a function of solution oxidizing power (electrode potential).
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Passivity

Fig. Corrosion characteristics of an active-passive metal as a function of solution oxidizing power (electrode potential).
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Passivity in Iron Chromium Alloys

Dissolution of an active metal (active dissolution), involves a charge transfer at the metal-electrolyte interface. Soluble ions, either hydrated or complexed, are formed and dissolve into the electrolyte, while the liberated electrons either flow to the cathode or are taken up by an oxidizing agent.

When a passive metal dissolves (passive dissolution), cations are formed by a charge transfer reaction at the metal-film interface. They migrate across the passive film to the film-electrolyte interface, where they dissolve into solution as hydrated or complexed ions.

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Cont

Because of the presence of an oxide film, the dissolution rate of a passive metal at a given potential is much lower than that of an active metal. It depends mostly on the properties of the passive film and its solubility in the electrolyte. During passivation, which is a term used to describe the transition from the active to the passive state, the rate of dissolution therefore decreases abruptly. The polarization curve of a stainless steel in sulfuric acid, given in Figure, illustrates this phenomenon. In this electrolyte, the corrosion potential of the alloy is close to 0.3 V. Anodic polarization leads to active dissolution up to about 0.15 V, where the current density reaches a maximum. Beyond this point, the current density, and hence the dissolution rate, drops sharply. It then shows little further variation with potential up to about 1.1 V. Above that value the current density increases again because transpassive dissolution and oxidation of water to oxygen becomes possible.

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Fig. Polarization curve of Fe-17Cr stainless steel in 0.5 M H2SO4. Sweep rate is 0.02 V/min.
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Generally speaking, we can distinguish three potential regions in the polarization curve of a passivating metal (Figure ): the active region; the passive region; the transpassive region. In contrast to the active and passive regions, the surface state of the metal in the transpassive region is not well defined and an oxide may or may not cover the surface.

Figure. Variation of partial anodic current density with potential for a passivating metal (Evans Diagram).
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The current density measured during a polarization experiment is the sum of all anodic and cathodic partial current densities. Figure . Schematically shows the variation of the anodic partial current density of a passivating metal as a function of the potential. It allows us to define a number of quantities that describe the polarization behavior of passivating metals. The passivation potential Ep separates the active from the passive potential region. The corresponding current density at the maximum is the passivation current density, ip. The passive current density ipp characterizes the dissolution behavior of the metal in the passive potential region. The transpassivation potential Eb marks the end of the passive potential region and the transition from passive to transpassive behavior. Beyond this point the anodic partial current density increases markedly with increasing potential due one of the following processes: uniform transpassive dissolution resulting from oxidation of the passive film, dissolution by pitting resulting from local film breakdown, oxygen evolution due to water oxidation.
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When dissolution by pitting is the dominating reaction, the potential Eb is called pitting potential or critical pitting potential. Often, Eb is also referred to as film breakdown potential, indicating that pitting is initiated by passive film breakdown.

Depending on conditions, the value of Eb can be either above or below the reversible potential of the oxygen electrode, Erev,O2. For sufficiently stable passive films with good electronic onductivity, oxygen evolution rather than transpassive dissolution may therefore account for the observed current at high anodic potentials. The pitting potential, plays an important role for the corrosion resistance of passive metals and alloys. Generally speaking, to have a good corrosion resistance an alloy should exhibit a low value of Ep and a high value of Eb.

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Figure Variation of passivation potential for Fe-Cr alloys with pH in sulfate solutions

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Generally, the oxides of less noble metals exhibit a lower standard potential of formation. These metals passivate spontaneously in the presence of protons. Furthermore, many oxides exhibit good chemical stability in acidic environments. This explains the higher corrosion resistance of metals such as titanium, tantalum and chromium. According to the relation,

the value of Erev,oxide decreases by 59 mV per pH unit, regardless of the stoichiometry of the oxide formed; this is because the number of charges does not appear in the equation. The condition Ep Erev,oxide, suggests that the passivation potential also decreases with increasing pH.

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Figure confirms this behavior: When the passivation potentials of iron, chromium and their alloys in sulfuric acid are plotted as a function of the pH, a straight line is obtained with a slope of 59 mV/pH. Similar results have been found for other metals. In this figure, for zero pH (pH = 0; Erev,oxide = E), the passivation potentials of chromium and iron do not match the standard potentials of the oxides Cr2O3 and Fe2O3 listed in Table 6.8. One explanation is that kinetic limitations lead to a higher passivation potential than predicted by thermodynamics. Another reason could be that the listed standard potentials were measured on bulk samples. The extreme thinness of passive films could influence their thermodynamic properties. In addition, their stoichiometry. composition does not always correspond to a simple

For example, chromium-iron alloys form passive films containing both iron and chromium cations and their passivation lie between those of iron and chromium. Then again, they exhibit the same pH dependence as the pure metals.
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Figure 6 Anodic polarization curves of Fe, Ni and Cr in 0.5 M H 2SO4

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In acidic media, the metals iron, nickel and chromium have passivation current densities that increase in the order Cr < Ni < Fe. In Figure 6, the anodic polarization curves for the three metals in 0.5 M sulfuric acid (25C)are compared. Chromium has lower values of both ip and Ep than the other two metals. By alloying increasing amounts of chromium to steel one therefore improves the corrosion resistance. Experience shows that above a chromium concentration of 12 to 13%, a steel passivates spontaneously in contact with aerated water. It becomes "stainless, meaning it does not rust easily

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Figure Corrosion potentials of Fe-Cr alloys in aerated 4% NaCl as a function of their chromium content. The measured average rate of corrosion in salt spray tests is also shown
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Corrosion potentials of iron-chromium alloys in an aerated solution of 4% NaCl together with the corrosion rate measured in a salt spray test. Spontaneous passivation above a chromium content of 8 to 12%, leads to a rise in corrosion potential and to a drop of corrosion rate. The magnitude of the passivation current density depends on different factors: the kinetics of active dissolution; the mass transport of the dissolution products; the pH of the electrolyte; the water content of the electrolyte.

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THANK YOU

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