Corrosion & Environmental Degradation

Corrosion & Environmental Degradation

Corrosion is a major cause of the deterioration of engineering structures, and has an associated cost that is about 5% of the gross national product. This implies
that corrosion control is an important consideration in the design process. The process is not only associated with large engineering structures, but is associated
with semiconductor devices and materials used to fabricate medical implants. Biocompatibility of implants involves material stability in the biological
environment as well as the non-toxic nature of the material and its corrosion products. This section will explore some of the fundamental reactions involved in
corrosion and strategies to minimize the corrosion process.

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Introduction
Electrochemical Processes
Electrode Potentials
Reaction Rate
Galvanic Cells
Crevice corrosion
Stress Corrosion
Pit Corrosion
Hydrogen Cracking
Protection Methods
: Passive Surface Films
Protection Methods II : Al, Stainless Steel, Ti
Biological Environments : Biological Corrosion , Orthopedic Implants

Introduction

Corrosion is a general term used to describe various interactions between a material and its
environment leading to a degradation in the material properties.
Interaction with ambient oxygen can cause the formation of oxide layers via diffusion controlled
growth. These may passivate the material against further oxidation.
In a wet environment, aqueous corrosion can occur due to electrochemical processes which
depend upon metal ion transport and reaction. Gradients of metallic and electrolytic ion
concentrations, temperature, ambient pressure, and the presence of other metals, bacteria, or
active cells, all influence the corrosion rate.
Electric fields applied to corroding systems can accelerate or inhibit the rate of corrosion or
material deposition. Galvanic corrosion between different metals in an aqueous environment is
due to the electric field arising from the different electrode potential of the two materials. External
fields may enhance or supress this corrosion.
In all of these reactions, electron and ionic transport occurs. The following sections will be
concerned with these processes and the effect of conditions on the corrosion rates.

Electrochemical Processes

The diagram illustrates an electrochemical reaction occurring at the surface of a metal covered
with a film of water containing dissolved oxygen. The two reactions involved in the corrosion are
shown. Metal atoms dissociate into metal ions and free electrons in the oxidation reaction at
the anode. These electrons migrate in the metal and initiate the reduction reaction at
the cathode that generates the hydroxyl ions.

The oxidation and reduction reactions are in

balance such that, for the case illustrated,
two metal ions go into solution for every four
hydroxyl ions produced. The slowest reaction
rate controls the overall corrosion rate.

Other reduction reactions are possible, and

several may occur simultaneously in a real
corrosion process

An example of the type of reaction show above is the corrosion of

environment containing H+ ions.
The zinc atoms will be
At the

oxidized at the anode in the reaction:

zinc in an oxygen- free acidic

Zn -> Zn

2+

+ 2e-

cathode, the hydrogen ions of the acidic electrolyte will be reduced to hydrogen gas:
2H+ + 2e- -> H2 (gas)

The overall corrosion reaction will be the sum of these two processes, provided no other reduction
reactions occur.
Zn + 2H+ -> Zn 2+ + H2 (gas) In this reaction, the products of the corrosion
process do not remain on the surface of the metal and corrosion will continue as long as the
conditions are maintained.
For

Iron corroding in oxygenated water (rusting), the corrosion products may remain on the surface of
the metal and change the corrosion rate as the reaction continues.

The overall rusting reaction has two steps.

First, iron is oxidized to the 2+ state in the reaction:

Fe + O + H2O -> Fe2+ + 2 OH _ -> Fe(OH)2

In the second step, the iron changes from a 2+ ion to a 3+ ion, generating an insoluble compound that
remains on the surface of the metal.
2Fe(OH)2 + O + H2O -> 2Fe(OH)3

The rust is non-metallic and interferes with further charge transfer from the metal.

 The above discussion indicates that metallic corrosion involves both oxidationat the anode that
generates a metal ion and free electrons: M -> M+n + ne andreduction processes that
consumes the electrons at the cathode.
The cathodic reactions listed below depend upon the nature of the corrosion environment but
share the common process of electron consumption (reduction). If more than one process can
occur, this will increase the overall corrosion rate.
Hydrogen ion reduction in an oxygen-free acidic environment is one possibility:
2H+ + 2e _ -> H2 (gas)

In an oxygenated acidic environment, oxygen reduction to water can occur:

O2 +4H+ +4e -> 2H2O
In a neutral or basic solution, hydroxyl ions may be formed by oxygen reduction:
O2 + 2H2O + 4e -> 4OHMultivalent metal ions in solution may be reduced by electron transfer:
M3+ + e -> M2+
Metal deposition on the cathode results from the reduction of ions in solution:
M+ + e -> M

https://www.princeton.edu/~maelabs/mae324/12/corrosion.htm