CORROSION ENGINEERING

Corrosion Principles Lecture No. 2

Samah Yousif

Lecture Content
Introduction How corrosion occurs? Thermodynamic principles of corrosion Kinetics principles of corrosion

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Corrosion Engineering - Lec 2

Introduction
Material selection is a critical decision in material fabrication.
The most important characteristics to be considered in material selection are: 1. Material properties 2. Temperatures effect on the mechanical properties 3. Corrosion resistance 4. Required properties 5. Ease of fabrication 6. Availability 7. Cost

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How corrosion occurs?

Environment is the key factor in any corrosion situation.
Practically, Environment refers to microenvironment condition or local environment.

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How corrosion occurs?

Corrosion occurs as a result of electrochemical reactions combined with an electrical current flows between anodes and cathodes.
As water and steels or iron-based alloys are commonly used industrially, they will be used for corrosion illustration.

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How corrosion occurs?

Metal ions go into solution at anodic areas by the following anodic reaction:

Fe Fe 2e

o Rapid reaction o Anode employing external current o Iron corrodes

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How corrosion occurs?

Free electrons combine with Hydrogen ions in the cathodic reaction:

2 H 2e H 2
o Slower reaction o Proceeds rapidly in acids, and slowly in alkaline or neutral media.

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How corrosion occurs?

If dissolved oxygen presents in the solution an oxygen reduction reaction will occur:

4H O2 4e 2H 2O

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How corrosion occurs?

Adding the anodic reaction to the oxygen reduction reaction, using ( H 2O H OH ), leads to:

2 Fe 2 H 2O O2 2 Fe(OH ) 2

o Where Fe(OH ) 2 is the Ferrous oxide, o White when pure, but green to greenish black after air oxidation.
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How corrosion occurs?

At the outer surface of the oxide film, access to dissolved oxygen converts ferrous oxide to hydrous ferric oxide:

4 Fe(OH ) 2 2 H 2O O2 4 Fe(OH ) 3
o Hydrous ferric oxide Fe(OH )3 is orange to redbrown in color and makes up most of ordinary rust.

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How corrosion occurs?

In summary, corrosion is an electrochemical process with two directions;
o Ions dissolving in the solution (oxidation or corrosion) o Ions precipitation in the metal (reduction)

These two processes continue until equilibrium achieved.

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How corrosion occurs?

1. 2. 3. Corrosion can be divided into: Aqueous corrosion Atmospheric corrosion Hot corrosion

The above mechanism is applicable only for aqueous and atmospheric corrosion where an electrolyte surrounds the metal. In high temperature corrosion only oxygen or gases surrounds the metal. In common, all corrosion types involve electrochemical reactions.
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How corrosion occurs?

For corrosion to occur, reactions must continue to maintain electrical equilibrium. The speed of reaction determines the speed and severity of corrosion and vice versa.
The speed of reaction is measured by the electrical current (Icorr), as shown in Evans Diagram.
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How corrosion occurs?

The necessary components to set up an electrochemical cell (Metallic corrosion): 1. Anode the corroding electrode. 2. Cathode the passive, non-corroding electrode. 3. The conducting medium the electrolyte the corroding fluid. 4. Completion of the electrical circuit through the material.
Cathodic areas can arise in many ways:
o o o o o o
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Dissimilar metals. Corrosion products. Inclusions in the metal, such as slag. Less well-aerated areas. Areas of differential concentration. Differentially strained areas.
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Thermodynamic principles in corrosion

Thermodynamics is used extensively in corrosion studies.
We will focus on:
o Free energy change (G) o pH effect o Potential difference and metal corrosion

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Thermodynamic principles in corrosion

Free energy change (G):
It is a quantitative measurement for reaction potential. o G<0 large tendency for reaction --- corrosion occurs o G=0 equilibrium o G>0 stable --- no corrosion

Q: How G is calculated for chemical and electrochemical reactions?

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Thermodynamic principles in corrosion

pH effect:
From thermodynamics: the tendency to form Fe2+ or Fe(OH)2 is a function of the pH.

Log[ Fe ] 13.4 2 pH
o Acidic solution (low pH), corrosion increases. o Alkaline solution (high pH), corrosion occurs slowly

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Thermodynamic principles in corrosion

Potential difference and metal corrosion:
o For corrosion to occur, the potential of the anodic reaction should be less than the cathodic reaction potential. o Therefore, corrosion can be predicted by using the EMF series, which shows the standard potential taking the hydrogen as 0.

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Thermodynamic principles in corrosion

Element Electrode Potential (V)

In the presence of hydrogen or oxygen:

o Does Au corrode? o Does Ag corrode? o Does Zn corrode?

Au O2

1.7 1.23

Pt
Ag Cu H2

1.2
0.8 0.34 0.0

Pb
Sn Ni Fe Cr Zn Al Mg

-0.13
-0.14 -0.25 -0.44 -0.74 -0.76 -1.66 -2.36
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Thermodynamic principles in corrosion

Thermodynamic principles can help explain a corrosion situation (stability of chemical species and reactions associated with corrosion processes). However, thermodynamic calculations cannot be used to predict corrosion rates.

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Kinetic principles in corrosion

Potential difference cannot indicate the speed of corrosion as kinetic factors might effect the corrosion rate. Eg. consider a Cu electrode immerged in CuSo4 solution, Cu Cu 2e o The anodic reaction: o The cathodic reaction: Cu 2e Cu
The reaction speed is estimated by Exchange Current Density (Io) = Ia - Ic. At equilibrium the speed of anodic and cathodic reactions are equal, thus Ia = Ic and Io = 0 (corrosion doesnt occur).
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Kinetic principles in corrosion

Corrosion occurs in the following cases: Case 1:
o Zn electrode connected to Pt electrode immerged in a solution contains hydrogen atoms.

Case 2:
o Zn electrode connected to Cu electrode in an electrochemical cell.
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Kinetic principles in corrosion

The speed of chemical reactions (corrosion) can be estimated by Faradays first and second laws .
The rate of corrosion can be calculated by: Where: R is the rate in mpy = mil per year (1mil = 0.001 inch) i = current density A/cm2 e = equivalent weight D = density of Metal, g/cm3

ie R 0.13 D

Prove!!
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Kinetic principles in corrosion

Factors affecting corrosion rate: 1- Metal properties:
o Purity, crystal structure, metal surface, internal stresses, etc

2- Surrounding environment:
o Solution concentration and components: pH, purity, O2 presence, o Solution flow speed o Solution temperature o Corrosion prevention o Start-up and shutdown
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END OF LECTURE 2

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