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CH.4.

PASSIVITY

Passivity y

A state of low corrosion rate due to the formation of a very thin surface films (1~10 nm) under oxidizing conditions with high anodic polarization ASTM G15: G15 Passive P i the th state t t of f a metal t l surface f characterized h t i db by l low corrosion rates in a potential region that is strongly oxidizing for the metal

Thermodynamically unstable, but possess a kinetic stability Fe, Ni, Cr, Al, Ti, Zr, Nb and their alloys.

Passivity y

Definition 1

A metal is passive if, on

increasing its potential to more positive values, the rate of dissolution decreases, exhibiting low rates at high potentials (thin-film passivity)

Definition 2

A metal is passive if it

substantially resists corrosion in an environment where there is a large thermodynamic driving force for its oxidation (thick-film passivity) Ex) Pb in acid, Mg or Al in H2O.

Pourbaix Diagram g for Fe

Image Source: http://www.crct.polymtl.ca/ephweb.php

Pourbaix Diagram g for Cr

Image Source: http://www.crct.polymtl.ca/ephweb.php

Pourbaix Diagram g for Al

Image Source: http://www.crct.polymtl.ca/ephweb.php

Pourbaix Diagram g for Ti

Image Source: http://www.crct.polymtl.ca/ephweb.php

Passivity y
O2

AP PPLIED POT TENTIAL (V)

NOBLE

transpassive

M xO y M

passive

M xO y M

EF Epp
active
M H2 M+

ACTIVE

ip ic log CURRENT DENSITY


Epp ic EF ip = primary passive potential = critical anodic current density = Flade Fl d potential i l = passive current density
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ActiveActive - Passive Corrosion Behavior

E Fe3+ Fe2O3 E Fe2+ eeq,H Ecorr Fe3O4 Fe 5 pH eeq,M

2H2OO2+4H++4eTranspassive

Passive

ipass
io,H /H (Fe)
+
2

MM++e-

Epp
Active dissolution

io,M M /M
+

icorr

2H++2e-H2 log |i|

Epp EM+Z/MxOy

Passivity y

Anodic polarization curves for iron and 304L stainless steel in 1N H2SO4

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ActiveActive - Passive Corrosion Behavior

Effect of increasing acid concentration and temperature on passivity.

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Corrosion Behavior of ActiveActive - Passive Metals


Case 1 : Point A Ecorr & icorr High h corrosion rate, not good d but b predictable. d bl ex) Ti in HCl or H2SO4 Case 2 : 3 points of f intersection at B, C, and D. point C is unstable. point B high icorr in the active region. point D low icorr = ip in the passive region. the least desirable case. ex) Cr in air free H2SO4, Fe in dilute nitric acid. Case 3 : One stable point E in the passive region. The metal will spontaneously be passivated. Most desirable system. ) stainless steels and Ti in acid solutions containing g oxidizers. ex) The nature and kinetics of the cathodic reactions (are) critical in determining the corrosion state and the rate of dissolution of an active-passive materials.

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Effect of Oxidizer Concentration

Hysterisis in Fig Fig. 4 4.6 6 indicates that the amount of oxidizer necessary to cause passivation is greater than that required to maintain passivity. To safely maintain passivity, oxidizer concentration should be greater than the minimum amount necessary to produce spontaneous passivation. In the borderline passivity region (GFEB), Any surface disturbance will destabilize the passive film and the corrosion rate increases.
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Effect of Oxidizer Concentration

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Effect of Solution Velocity y

Corrosion of stainless steel in a dilute acid solution such as seawater


passivated by p y an increase in solution velocity. y

The smaller the critical anodic current density (icrit), the easier a metal will be

Criteria for Passivation: Lower icrit and more active Epp is desirable.
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Summary y - Passivation
The rate of corrosion will be critically When a stable passive film has formed, affected by the cathodic curve the current has a steady, low value Rapid rate of cathodic reaction leads the passive current density to passivation, and low rate of Electrode P Potential corrosion But it may also lead to low rate of corrosion? rate of cathodic reaction Very Lower slow cathodic reaction leads to leads Current falls the passive starts Active corrosion gives normal activation to activity, and high rate of film corrosion low rate ofas corrosion to form - the active-passive active passive transition polarization

log |current density|

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Polarization Behavior of ActiveActive - Passive Alloys


(1) Galvanostatic () polarization curve Galvanostatic methods are not adequate for determining the active - passive behavior ; Above icrit, iapp no longer follows the anodic curve in the passive region, but jumps into the transpassive region and oxygen is evolved from the metal surface. (2) Potentiostatic () polarization curve Using a potentiostat, potential is increased from Ecorr in the active state in steps t with ith current t recorded d d at t th the end d of f an appropriate time at each step. At potentials above Epp, the potentiostatic anodic polarization curve exactly follows the passive loop of anodic curve. (e.g., a step rate of 50 mV every 5 min)
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Polarization Behavior of ActiveActive - Passive Alloys


Potentiodynamic polarization curve ( )

Potentiostat is p programmed g to increase potential p continuously y from Ecorr to


desired potential. (e.g., 0.6 V/h) Most anodic polarization curve are now obtained potentiodynamically.

Image Source: ASTM G5-94

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Polarization Behavior of ActiveActive - Passive Alloys

Anodic Current E Cathodic (Current) Loop Ecorr

Anodic Current ioM/M ioM/M log |i|

log |i|

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Polarization Behavior of ActiveActive - Passive Alloys

Activation-controlled Transpassive Oxygen corrosion of Active-passive Active peak passive fortransition iron Overall anodic curve dissolution reduction Cr

log |i|
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Polarization Behavior of ActiveActive - Passive Alloys

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Polarization Behavior of ActiveActive - Passive Alloys

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Application of Potentiostatic (Potiodynamic ( Potiodynamic) ) Anodic Polarization Technique


To judge the corrosion resistance of alloys and the corrosivity of solutions.

The result can be obtained in a few hours.

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Alloy y Evaluation
D C B A 3

A B C D

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Solution Corrosivity y

Dependence of Epit on [Cl-] Epit = A log [Cl-] + B Epit = 0.168 - 0.88 log [Cl-] (304 stainless steel) Epit= 0.05 - 0.124 log [Cl-] (Al) Minimum conc. of [Cl-] necessary for pitting

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Limitation

The growth and dissolution of the passive film is dynamic (Fig. 4.13) Polarization curve cannot be used as a quantitative guideline for long-term corrosion resistance Plant conditions are difficult to characterize and duplicate in the laboratory. laboratory Provide useful preliminary guidelines for more extensive in-plant exposure tests tests.

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Using g Passivity y to Control Corrosion


1. 2. A current can be applied by means of a device (a potentiostat) which can set and control the potential at a value greater than the passivating potential Ep. This method of producing passivity is called anodic protection. protection For environments containing the damaging species such as Cl- that cause local corrosion, the potentiostat or other devices that control the potential can be used as in 1 above to set the potential to a value in the passive region below the critical potential for pitting Epit. All Alloys or metals t l that th t spontaneously t l f form a passive i fil film, for f example, l stainless t i l steels, t l nickel, or titanium alloys, can be used in applications that require resistance to corrosion. Usually a pretreatment such as that described in tactic 4 below is desirable. A surface pretreatment can be carried out on an alloy capable of being passivated. The use of such a pretreatment has been as a standard practice for stainless steels for many years. The passivating procedure involves immersion of thoroughly degreased stainless steel parts in a nitric acid solution followed by a thorough rinsing in clean hot water. The most popular solution and conditions of operation for passivating stainless steel is a 30min immersion in a 20 vol % nitric acid solution operating at 1200F (490C). C) However, However other solutions and treatments may be used, depending on the type of stainless being treated. The environment can be modified to produce a passive surface. Oxidizing agents such as chromate and concentrated nitric acid are examples of passivating solutions that maintain a passive state on some metals and alloys.
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3 3.

4.

5.

Alloy y Selection

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Anodic Protection

Application of DC power to maintain the metal showing activepassive transition behavior in a passive state. passive

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Anodic Protection

Pot tential

Current Density (log i)

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Anodic Protection

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Anodic Protection

Any situation in which a active-passive behavior is a potential candidate for anodic protection if a corrosion problems arises. Mild steel or SS in sulfuric acid (conc. H2SO4) storage tanks, and to a lesser extent extent, coolers and piping piping. Mild steel in certain fertilizer solutions Mild steel liquor tanks in pulp and paper industries.

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Combination of CP and AP ( (Acid Cooler) )

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Alloy y Evaluation

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Effect of Alloying y g Elements


Ni Cr S, Mn, Al

Cr, Ni, W, , Ti

Mo, V

Ni, Mo, Cu

Cr
Cr, Ni, Mo, Cu, Nb, Ti

Cr, Ti

S, Mn

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Properties p of Passive Films


Oxide film theory

The passive film is always a diffusion-barrier layer of reaction products, for example, metal oxide or other compound which separates metal from its environment and which slow down the rate of reaction. reaction

According to this model, the following processes are driven by the electric field across the film. Entry of metal atoms into the film as cations at the metal-film interface Transport of the metal cations or of oxygen anions through the oxide. Dissolution of metal cations from the film at the film/environment interface. Properties required for protective passive film Stability over a wide potential range Mechanical integrity Low ionic conductivity Good electron conductivity to reduce the potential difference across the film Low solubility and slow dissolution in the aqueous medium.

Adsorption d i theory h

A chemisorbed layer of oxygen displaces the normally adsorbed H2O molecules and slows down the rate of anodic dissolution involving hydration of metal ions. Adsorbed oxygen decreases the exchange current density. M + (H2O)ads M(O2- adsorbed anion) + 2H+
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References

Textbook (D.A. Jones) R.G. Kelly, J.R. Scully, D.W. Schoesmith and R.G. Buchheit, Electrochemical Techniques in Corrosion Science and Engineering, Marcel Dekker Inc., New York, 2002. M.G. Fontana, Corrosion Engineering, 3rd ed., McGraw-Hill, 1987. Homepage for Prof. Kwons Laboratory, http://corrosion.kaist.ac.kr Lecture Notes by Dr. D.H. Lister, and Dr. W. Cook, Department of Chemical Engineering, University of New Brunswick. J.I. Munro and W.W. Shim, Mater. Perf., May (2001) 104. P.R. Roberge, Handbook of Corrosion Engineering, McGraw-Hill, New York, 2000. , JIS -,, 1994. 1994

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Homework Problems

Problems 1, 2, 3, 5, 9, 11 of Chapter 4 in textbook.

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