Corrosion Basics - An Introduction, 3rd Edition

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Table of Contents
Abbreviations
Preface to the Third Edition
PART I: WHAT IS CORROSION?
1. Scope and Language of Corrosion

1.1. What is Corrosion?
1.2. Purpose of this Book
1.3. Historical Perspective
1.4. References
2. Electrochemistry of Corrosion
2.1. Introduction
2.2 Why Metals Corrode
2.3 Corrosion Factors
2.4 Chemistry of Corrosion
2.5. Principles of Electrochemistry Applied to Corrosion
2.6. Corrosion Thermodynamics
2.7 Corrosion Kinetics
2.8. Application of Electrochemical Techniques in Corrosion
2.9. References
PART II: ENVIRONMENTS
3. Atmospheric Corrosion
3.1. Introduction
3.2. Types of Corrosive Atmospheres
3.3 Factors Affecting Atmospheric Corrosion
3.4. Measurement of Atmospheric Factors
3.5. Classification Schemes
3.6. Atmospheric Corrosion Tests
3.7. Corrosion Behavior and Resistance
3.8. References

4. Corrosion by Water and Steam
4.1. Introduction
4.2. Water Constituents
4.3. Types of Water
4.4. Scaling Indices
4.5. Cooling Water Systems
4.6. Steam Generating Systems
4.7. Water Treatment
4.8. References
5. Corrosion in Soils
5.1. Introduction
5.2. Corrosion in Soils
5.3. Microbiologically Influenced Corrosion (MIC)
5.4. References
6. High Temperature Corrosion

6.1. Introduction
6.2. The Materials
6.3. Basis of Corrosion Resistance
6.4. Corrosion Products
6.5. Corrosion in Air
6.6. Other Gaseous Media
6.7. Molten Phases
6.8. Corrosion in Liquid Metals
6.9. Corrosion in Vacuum
6.10. Mechanical Behavior
6.11. References
PART III: MATERIALS AND HOW THEY CORRODE
7. Engineering Materials
7.1. Introduction
7.2. Materials Selection
7.3. Corrosion Behavior of Metals and Alloys
7.4. Reinforced Concrete
7.5. Polymeric Materials
7.6. Other Nonmetals
7.7. References
8. Forms of Corrosion
8.1. Introduction
8.2. Uniform Corrosion
8.3. Localized Corrosion
8.4. Flow-Induced Corrosion
8.5. Mechanically Assisted Corrosion
8.6. References
9. Failure Analysis and Design Considerations

9.1. Making Choices Based on Economic Calculations
9.2. Rudiments of Corrosion Failure Analysis
9.3. Information to Look For
9.4. Design for Corrosion Service
9.5. References
PART IV: METHODS OF CONTROL
10. Protective Coatings

10.1. Types of Coatings
10.2. Why Coatings Fail
10.3. Soluble Salts and Coating Failures
10.4. Economic Aspects of Coatings Selection and Maintenance
10.5. Organic Coatings
10.6. Temporary Preservatives
10.7. Inorganic (Nonmetallic) Coatings
10.8. Metallic Coatings
10.9. Coating Inspection and Testing
10.10. Surface Preparation
10.11. References
11. Cathodic Protection

11.1. Historical Notes
11.2. How CP Works in Water
11.3. How CP Works in Soils
11.4. How CP Works in Concrete
11.5. Cathodic Protection Components
11.6. Potential to Environment
11.7. Current Requirement Tests
11.8. Stray Current Effects
11.9. Monitoring Pipeline CP Systems
11.10. Simulation and Optimization of CP Designs
11.13. References
12. Corrosion Inhibitors

12.1. Introduction
12.2. Types of Inhibitors
12.3. Basic Concepts
12.4. Environmental Factors
12.5. Green Inhibitors
12.6. Application Techniques
12.7. Safety Precautions
12.8. References
PART V: TESTING AND MONITORING
13. Corrosion Testing and Monitoring

13.1. Introduction
13.2. Corrosion Testing
13.3. Corrosion Monitoring
13.4. References
Appendix A. SI Units Conversion Table
Index

Abbreviations
ABS Acrylonitrile-butadiene-styrene
AC Alternating current
AE Acoustic emission
AIWJ Abrasive injected water jetting
ACS American Chemical Society
ASM American Society for Metals
ASTM American Society for Testing Materials
AWJ Abrasive water jetting
AWWA American Waterworks Association
BOD Biological oxygen demand
CLIMAT Classify Industrial and Marine ATmosphers
CCSRE Copper/copper sulfate reference electrode
CCVT Closed-cycle vapor turbogenerators
CDA Corrosion-damage algorithm
CFA Component failure analysis
CHC Cyclohexylamine carbonate
CIPS Close-interval potentials survey
COD Chemical oxygen demand
CP Cathodic protection
CPE Constant-phase element
DC Direct current
DCVG Direct-current voltage gradient
DHN Dicyclohexylamine nitrite
DO Dissolved oxygen
DOT U.S. Department of Transportation
DSA Dimensionally stable anodes
ECM Electrochemical machining
ECS Electrochemical Society
EDM Electrical discharge
EFSM Electrical-field signature method
EIS Electrochemical impedance spectroscopy
EMF Electromotive force
EN Electrochemical noise
EPR Electrochemical potentiodynamic reactivation
ER Electrical resistance
EVS Extreme value statistics
FN Ferrite number
GCP Galvanic cathodic protection
GFRP Glass-fiber-reinforced polymer
GDP Gross domestic product
GNP Gross national product

HAZ Heat-affected zone
HF Hydrofluoric (acid)
HIC Hydrogen-induced cracking
HPC High-performance concrete
HSLA High strength, low alloy
HT/HP High temperature/high pressure
IAP Ion-activity product
ICCP Impressed current cathodic protection
IGSCC Intergranular stress corrosion cracking
ISO International Organization for Standardization
ISO CORRAG International Organization for Standardization atmospheric-exposure program
KK Kramers-Kronig transforms
LMC Liquid-metal cracking
LPR Linear polarization resistance
LSI Langelier saturation index
MEK Methyl ethyl ketone
MIC Microbiologically influenced corrosion
MIL Military
NACE National Association of Corrosion Engineers
NDE Nondestructive evaluation
NHE Normal hydrogen electrode
OEM Original equipment manufacturer
PB Pilling-Bedworth ratio
PE Polyethylene
PH Precipitation hardening
PREN Pitting-resistance equivalent number
PSI Puckorius scaling index
PVC Polyvinyl chloride
PWR Pressurized-water reactors
RCA Root-cause analyses
RCI Root-cause investigation
RH Relative humidity
%RH Percent relative humidity
RSI Ryzner stability index
SAE Society of Automotive Engineers
SCC Stress corrosion cracking
SCE Saturated calomel electrode
SEM Scanning electron microscopy
SHRP U.S. Strategic Highway Research Program
SL Saturation level
SRB Sulfate-reducing bacteria
SSC Sulfide stress cracking
SSCE Saturated silver chloride electrode
SSPC Society of Protective Coatings
SHE Standard hydrogen electrode
TCA Trans-cinnamaldehyde

TDS Total dissolved solids
TFE Polytetrafluoroethylene
TLA Thin-layer activation
TOW Time of wetness
UHP AB Ultrahigh-pressure abrasive blasting
VCI Volatile corrosion inhibitors
VPI Vapor-phase inhibitors
WECS Working Environmental Corrosion Standards
ZPC Zero point of charge
ZRA Zero-resistance ammeter

Preface to the Third Edition
In the Preface to the first edition, one can read that this book, originally issued as notes
for the Basic Corrosion Course in 1970, has been through thirteen printings to support
the great number of people interested in the subject. As envisioned by the editor in the
Introduction of the original book, some revisions would be necessary with the passage
of time. In the 1984 revision, much of the material written by the original authors was
retained. Changes were made where it was believed that better continuity, less
repetition, and more recent data would improve the development of the subject. Those
responsible for the 1984 revisions were C. P. Dillon, J.S. Snodgrass, L.S. Van Delinder,
and H.A. Webster.
However, the authors of the first edition provided such excellent coverage of the subject
matter that only some rearranging and updating was necessary until the second edition,
produced in 2006.
When the NACE International Publication Committee became interested in updating this
popular textbook, they discussed a few options and decided to prepare the second
edition with a single author as the most efficient way of preserving this historical
document. I hope you find for yourself that this has been realized. My main goals
throughout this daunting project were to respect and keep the spirit of the first edition
and maintain the quality of the information it conveyed, while bringing all these
interesting subjects into the twenty-first century.
This book provides general coverage of the wide field of corrosion control. It is
designed to help readers being initiated into corrosion work and presents each
corrosion process or control procedure in the most basic terms. As mentioned in the
Preface to the first edition, the original material was first published in 1970. While
corrosion principles have not changed much since the lecture notes from the late 1960s
were assembled to create the first edition, there have been major advances and changes
in the technologies used to combat corrosion damage.
Education in corrosion control was the primary concern and motivation behind the first
lectures. It was again the primary focus during the production of the first edition. My
thirty-five years of teaching corrosion and materials engineering, in addition to
seventeen years as webmaster of the Corrosion Doctors website, have helped me keep
the focus for the second and now third editions.

Besides a complete reorganization of the order in which material is presented, and the
addition of sections about electrochemistry and reinforced concrete, readers will find
that the new text uses SI units in compliance with NACE International policy. Appendix
A presents a conversion table for many non-SI units that some readers may find useful.
Finally, I would like to express my gratitude to all the reviewers who have diligently
helped to improve the book and particularly to Ken Tator and J.P. Broomfield for their
great help with the chapters on protective coatings and reinforced concrete,
respectively.
P.R. Roberge, main author/editor of the 2nd (2005) and 3rd (2017) editions

part I
What Is Corrosion?

1
Scope and Language of Corrosion
1.1. What is Corrosion?

“Since the first day that man, through his ingenuity, contrived to reduce metallic ores to
useful engineering materials, he has been constantly confronted and challenged by those
fundamental laws of nature, that, through the process of corrosion tend to convert those
useful metals back to the state in which they were first discovered.” This citation, from
one of the first issues of the journal CORROSION, still rings very true today [1].
Most people are familiar with corrosion in some form or another, particularly the
rusting of an iron fence or a tin can, the degradation of steel pilings or boats and boat
fixtures, or the rusting of common nails. However, invisible rusting often leads to
surprises as exemplified in Figure 1.1, which shows a city lamppost fallen on a windy
day due to the corrosion of its steel base. Piping is another major type of equipment
subject to corrosion. This includes water pipes in the home, where corrosion attacks
mostly from the inside, as well as the underground water, gas, and oil pipelines that
crisscross our land.

Figure 1.1. City lamppost fallen due to corrosion of its base (Figure courtesy of
Bruce Hector, Rust Check Kingston)
A dramatic presentation of corrosion problems was recently published, in which the

journalist qualifies the degradation of metals we call corrosion as the worst natural
disaster of all, being costlier than all other natural disasters combined [2]. Thus, it
would appear safe to say that almost everyone is at least somewhat familiar with
corrosion, which is defined in general terms as the deterioration of a substance, usually
a metal, or its properties because of a reaction with its environment.
The words chemical and electrochemical are not used in this definition. This general
definition recognizes that materials other than metals or alloys may corrode. The
deterioration of wood, ceramics, polymeric materials or “plastics,” and other materials
must also be studied by the corrosion engineer, and are included in the term corrosion.
This definition also indicates that material properties, as well as the materials
themselves, can and do deteriorate. With some forms of corrosion, there is no weight
change or visible deterioration, yet properties change and the material may fail
unexpectedly because of certain changes within it. Such changes may defy ordinary
visual examination or weight change determinations. These are nevertheless important
forms of corrosive action with which a corrosion engineer should be familiar.
1.2. Purpose of this Book

As with the first and second editions of “Corrosion Basics: An Introduction,” this third
edition is intended to convey the scope of the field of corrosion prevention and control.
It is important to realize the extent of the effort being made today in analyzing and
combating corrosion. Much of the experience and many of the workable solutions
developed in one area of corrosion work can be used to improve the control procedures
of another area. While most people work in only one area of this total discipline, there
is always the possibility that a shift in responsibilities or interest brings one to work in
a completely different area of corrosion prevention and control.
Many become engaged in controlling or preventing corrosion by appointment rather than

as the final step in a formal education with corrosion prevention as its original goal.
This book is therefore designed to be helpful to that segment entering this field without
the benefit of any extensive training in the basic sciences related to corrosion, but who
may be called upon from time to time to take at least the first steps in anticipating,
diagnosing, and otherwise dealing with corrosion problems, either on their own or in
collaboration with others.
Like any other technical discipline, corrosion work uses certain words, methods of
presenting data, and shorthand symbols that are peculiar to the field. This book reveals
this jargon in a manner that should, in the future, allow you to read or discuss corrosion
topics with greater understanding and confidence.
The best techniques available for detecting corrosion, determining the corrosion
resistance of a material, or evaluating the efficacy of a control procedure serve as daily
tools for attacking the problems faced by thousands of persons engaged in corrosion
work. This book will foster a better appreciation for these procedures.
Certainly, anyone concerned with corrosion work is primarily interested in control

procedures that allow the safe, economic use of a material in a specific environment.
Thus, basic aspects of the most current control techniques are described. After learning
the elements of each procedure, one can further investigate the possibility of using these
approaches to solve specific problems. For instance, it could be found that cathodic
protection (Chapter 11), which in many instances can halt corrosion by the throw of a
switch, could be adapted to solve other specific problems of interest.
A modern corrosion engineer or technician must find suitable materials for a great
variety of corrosive environments and temperature ranges, and be familiar with the
behavior of numerous alloys, as well as possible substitutes nonmetallic materials.
However, since metals have and will undoubtedly continue to be the major engineering
materials of concern, the focus of this book is mostly on the corrosion behavior of
metals.
Ask the general question “In what environments does corrosion occur?” The only
suitable answer is, “In just about any environment, depending on the material being
used.”
Another general question that often arises is, “How many forms of corrosion are there?”
Again, the answer may be unexpected. Some may say two or three, others propose eight,
and still others more safely say, “Quite a few!” These forms of corrosion are discussed
in detail in Chapter 8.
1.2.1. Economic and Societal Significance

Since the first significant report by Uhlig in 1949 that the cost of corrosion to nations is
indeed great [3], the conclusion of all subsequent studies has been that corrosion
represents a constant charge to a nation’s gross national product (GNP). In Uhlig’s
report, the annual cost of corrosion to the U.S. was estimated to be $5.5 billion, or 2.1%
of the 1949 GNP. This study attempted to measure the total costs associated with
corroding components by summing up the cost both for the owner and operator (direct
cost) and for the users (indirect cost).
Cost-of-corrosion studies of various forms and importance have since been undertaken
by several countries including the United States, the United Kingdom, Japan, Australia,
Kuwait, Germany, Finland, Sweden, India, and China [4]. The common finding of these
studies was that the annual corrosion costs ranged from approximately 1–5% of the
GNP of each nation. Several studies separated the total corrosion costs into two parts:
1. the portion of the total corrosion cost that could be avoided if better corrosion
control practices were used, and
2. costs where savings required new and advanced technology (currently unavoidable
costs).
Estimates of avoidable corrosion costs varied widely, ranging from 10–40% of the total
cost. Most of the studies allocated corrosion costs to industrial sectors or to categories
of corrosion control products and services. All studies addressed direct costs. A

common conclusion was that the indirect costs, due to corrosion damage, are often
significantly greater than the direct costs. Indirect costs were more difficult to estimate.
Potential savings and recommendations for ways to realize the savings were included in
most of the reports as formal results or as informal directions and discussion. Two of
the most important and common findings were
1. better dissemination of the existing information through education and training,

technical advisory and consulting services, and research and development
activities, and
2. the opportunity for large savings through the more cost-effective use of currently
available means to reduce corrosion. Most studies addressed only the magnitude of
possible savings without identifying the means of realizing such savings.
The most recent study resulted from discussions between NACE International
representatives, members of the U.S. Congress, and the Department of Transportation
(DOT). An amendment for the cost of corrosion was included in the Transportation
Equity Act for the 21st Century, which was passed by the U.S. legislature in 1998. The
amendment requested that a study be conducted with an interdisciplinary team of experts
from the fields of metallurgy, chemistry, economics, and others, as appropriate.
Two different approaches were taken in the ensuing study to estimate the cost of
corrosion:
• The first approach followed a method where the cost is determined by summing the
costs for corrosion control methods and contract services. The costs of materials
were obtained from various sources, such as the U.S. Department of Commerce
Census Bureau, existing industrial surveys, trade organizations, industry groups, and
individual companies. Data on corrosion control services, such as engineering
services, research and testing, and education and training were obtained primarily
from trade organizations, educational institutions, and individual experts. These
services included only contract services and not service personnel within the
owner/operator companies.
• The second approach followed a method where the cost of corrosion was first
determined for specific industry sectors and then extrapolated to calculate a national
total corrosion cost. Data collection for the sector-specific analyses differed
significantly from sector to sector, depending on the availability of data and the form
in which the data were available. To determine the annual corrosion costs for the
reference year of 1998, data were obtained for various years in the surrounding
decade, but mainly for the years 1996–1999.

The total cost due to the impact of corrosion for the individual economic sectors was
$137.9 billion per year (Table 1.1). A breakdown of these costs by individual sectors is
shown in Figure 1.2. Since not all economic sectors were examined, the sum of the
estimated costs for the analyzed sectors did not represent the total cost of corrosion for
the entire U.S. economy. By estimating the percentage of U.S. GDP for the sectors for
which corrosion costs were determined and by extrapolating the figures to the entire
U.S. economy, a total cost of corrosion of $276 billion was estimated (Figure 1.3). This
value shows that the impact of corrosion is approximately 3.1% of the Nation’s GNP
(Figure 1.3). This cost is considered to be a conservative estimate, since only well-
documented costs were used in this latest study. Other costs of corrosion were
discussed (not estimated) in the individual sectors, but were left out due to lack of
documentation.

Figure 1.2. Percentage contribution to the total cost of corrosion for the five sector
categories

Figure 1.3. Total direct annual cost of corrosion
Table 1.1. Summary of estimated direct cost of corrosion for industry sectors
analyzed (2001 study)

The indirect cost of corrosion was conservatively estimated to be equal to the direct
cost; giving a total direct plus indirect cost of $552 billion (i.e., 6% of the GDP).
Evidence of the large indirect corrosion costs are
1. Lost productivity because of outages, delays, failures, and litigation

2. Taxes and overhead on the cost of the corrosion portion of goods and services
3. Indirect costs of non-owner/operator activities
In October 2014, NACE International initiated a new study to examine the role of
corrosion management in establishing industry best practices [5]. The IMPACT study
provides an update on the global cost of corrosion. The study also assesses corrosion
management practices across various industries and countries, provides a template for
corrosion management in the form of a Corrosion Management System (CMS)
framework and guidelines, and provides financial tools that can be used for calculating
life-cycle costs and return on investment (ROI).
The fact that corrosion control typically produces a cost-benefit return is a lesson
learned over and over again by industry, often too late and following catastrophic events
such as accidents, failures, and loss of production. To achieve the full extent of potential
savings, it is the conclusion of this study that implementing a CMS and its integration
into an organization’s overall management system is mandatory.
1.2.2. Corrosion Around Us

All metals and alloys can and generally do corrode. The following are some examples
of common objects and areas susceptible to corrosion.
1. The automobile is a veritable corrosion-testing device. Materials must be selected

for use for atmospheric, high-temperature, closed cycle water, wear, fatigue, and
crevice exposures. Many different metals, polymeric materials (e.g., plastics),
paints, metallic coatings, and inhibitors are used to prolong the life of the parts.
However, the body, and certainly the muffler are generally seen in various stages of
corrosion. In fact, when examining a car over seven years old, it is often not
necessary to look under the car, just looking at the car’s body will probably reveal
corrosion taking place in numerous locations.
2. According to the US Census Bureau, the American electronic manufacturing
industries alone shipped $336 billion worth of electronic components in 1997. The
trend toward technological miniaturization has led to the development of small
personal electronic devices that are now present everywhere, such as pagers, cell

phones, and palm-sized personal organizers and computers [6]. In the presence of
moisture and an electric field, silver ions can migrate to a cathodically (negatively)
charged surface and plate out, forming dendrites. The dendrites grow and
eventually bridge the gap between the contacts, causing an electric short and
possibly arcing and fire. Even a small volume of dissolved metal can result in the
formation of a relatively large dendrite (Figure 1.4).

Figure 1.4. Dendrite on a circuit board after its exposure in a test chamber (Figure
courtesy of David A. Douthit, LoCan LLC)
3. In looking at the water pipes of an older home, particularly if they are made out of
steel or even galvanized steel, some corrosion is usually evident, particularly at the
joints where the galvanized coating might have been cut or at a junction where a
brass valve has caused heavy corrosion in the adjacent area.
4. Barnyard roofs made of steel or galvanized iron rust through in time, whereas the
properly-chosen aluminum roofs look bright and shiny and appear to be free of
corrosion much longer.

5. Kitchen utensils generally look bright and shiny, although their interiors are often
stained below the water line and sometimes pitted.
6. The green patina on copper or brass roofs of churches and government buildings
develop as a result of corrosion. Copper-bearing metals that have reacted with
certain components of the atmosphere develop this patina, which is actually
considered a protective layer that retards any further reaction and is also pleasing
to the eye.
7. Various industries, particularly petroleum and chemical companies, have numerous
corrosion problems unique to their operations. The average person is probably
totally unaware of them. Such companies generally maintain a corrosion-conscious
staff to keep the plants out of trouble.
8. In the case of an aluminum canoe, corrosion seems almost negligible, although a
close look often reveals tiny pits of corrosive attack that eventually can produce
water leaks.
9. Metals exposed to seawater may corrode heavily. Ship hulls (inside and out),
piling, oil rig platforms, equipment for fresh-water recovery, and other items
exposed to this highly corrosive environment must be protected in some manner.
Luckily, most types of corrosion control may be used in seawater.
10. Concrete degradation of bridges, highways, buildings, and drainage ducts is often
caused by reaction with the environment rather than by mechanical forces. When
corrosion control is not exercised during initial construction, taxpayer money is
often required for the restoration of the failed facilities.
11. Many houses in the nation have cold-water lines, vent and drain ducts, moldings,
and other construction components that are made of plastic materials. These have
been successful, but how many people are aware of their limitations, how to use
them, and the differences in performance between the available materials?
12. A person may drive along a roadway and see a metal box at the fence line along the
road right-of-way marked something like, “XYZ Gas Co. Do Not Disturb.” While
this may not be much of a clue to most people, it probably indicates a test point
installation that allows the corrosion-control personnel to measure the corrosion
protection being provided for a steel pipe many feet below the surface through a
process called cathodic protection (Chapter 11).
Other common examples of corrosion, either occurring or under obvious control are
observed by everyone each day. I hope this book will aid in more intelligent
observation of these phenomena.
1.2.3. Choosing the Right Material

Of the 103 elements in the Periodic Table shown in Figure 1.5, approximately 80 are
metals, each possessing different mechanical, chemical, and physical properties.
Although all of these metals can corrode, they do it in many different manners.
Furthermore, many of these 80 metals have been alloyed to make tens of thousands of
different alloys.

Figure 1.5. Periodic Table of the Elements
Note: Elements in the periodic table are arranged in periods (rows) and
groups (columns). Each of the seven periods is filled sequentially by the
atomic number. Groups include elements having the same electron
configuration in their outer shell, which results in group elements sharing
similar chemical properties. The lanthanides and actinides are actually a
part of periods 6 and 7, respectively.
Obviously, one person cannot memorize the composition of such a large number of
alloys. Reference texts are available to provide such information. Chapter 7 contains a
general description of the mechanical properties and chemical composition, as well as
the corrosion characteristics of the most commonly used alloys. Chapter 7 also
introduces some nonmetal materials an engineer has to consider for specific
applications. In many situations these often newer materials combine gracefully with
metals to provide strength, endurance, and light weight at an advantageous cost.

1.2.4. Defining the Environment
The fact that corrosion does occur should not be cause for surprise. Almost all materials
should be expected to deteriorate with time when exposed to the elements. Corrosion is
a perfectly natural process, as natural as water flowing downhill. If water flowed uphill
or remained stationary on a hillside, there may be cause for surprise, yet our human
ingenuity can accomplish this by putting water in a closed container (pipe) and closing
the bottom end, or by merely freezing it.
Similarly, if iron or steel is exposed to air and water, rust can be expected to develop
within a matter of hours. In fact, it would be surprising if the exposed iron did not
corrode or rust. Of course, if copper, brass, aluminum, or stainless steel was substituted
for iron, a given degree of corrosion might take longer, but some corrosion is still
anticipated. Instead of forming rust (a form of iron oxide), some oxides of copper,
aluminum, or chromium may form very slowly and coat the bare metal. This oxide
coating, even if extremely thin, could form a partial barrier to continued attack and slow
down the rate of corrosion to almost a standstill.
A surface-layer formation, whether it is oxide, carbonate, sulfate, or any other

compound, is a major factor in corrosion resistance, particularly if the layer effectively
separates the underlying metal from its environment. Such a naturally formed coating
must be diffusion- and moisture-resistant to be effective. Ordinary iron does not
naturally form an effective barrier; its rust permits oxygen and moisture to penetrate and
continue rusting. Thus, unless precautions are taken, failure will eventually occur.
Precautions to prevent iron and its alloys from corroding constitute a major effort in
corrosion control. It is here that we often resort to the use of protective coatings over
the metallic surface to prolong its useful life. Other techniques that form the basis of
modern corrosion control are discussed in later chapters.
Some metals, like stainless steel, titanium, or aluminum, are frequently left unpainted.
This is not because these metals are inert, but because oxygen in the air helps develop a
protective oxide layer on the metallic surface. Although these oxide layers are so thin as
to be invisible to the eye, they can be detected and their presence verified.
Some environments are more corrosive than others. While there are exceptions, the
following statements are generally accepted as facts.
1. Moist air is more corrosive than dry air.

2. Hot air is more corrosive than cold air.
3. Hot water is more corrosive than cold water.
4. Polluted air is more corrosive than clean air.
5. Acids are more corrosive than bases (alkalies) to steels.
6. Salt water is more corrosive than fresh water.
7. Stainless steel will outlast ordinary steel.
8. No corrosion will occur in a vacuum, even at very high temperatures, etc.
While it may be a surprise to some, there are instances when all of the above statements,
including the last one, are incorrect. This indicates that broad, categorical statements
regarding corrosion should be considered to be suspect. There is essentially no
statement regarding corrosion or the use of a material that does not have an exception.
1.3. Historical Perspective

Organized studies have been devoted to corrosion for a longer time than most people
realize. The British Association for the Advancement of Science appropriated a sum of
money for a series of corrosion experiments on the corrosion of cast and wrought iron in
the 1830s. Experiments were conducted by Robert Mallet and reported by him in 1838,
1840, and 1843. Mallet’s work was done in an era in which gifted scientists were
investigating the properties of matter.
Many interesting references and reflections on historical aspects of corrosion can be

found in the special Symposium that was held to celebrate NACE International’s fiftieth
anniversary [7]. Table 1.2 presents some historical landmarks of discoveries related to
the understanding and management of corrosion.
Table 1.2. Historical landmarks of discoveries related to the understanding and

management of corrosion

The science of corrosion has had two periods of rapid advancement. One, in the first
half of the nineteenth century, was a result of intense and sustained scientific interest and
activity aroused by the invention of the galvanic battery and the controversy over the
nature and source of the galvanic current. The other, in the first half of the twentieth
century, was stimulated by the growing realization of the immense economic cost of
corrosion in a rapidly developing industrial age. In the latter period, a number of
theories and facts established in the earlier one were rediscovered or elaborated, or
both. These include the electrochemical theory of corrosion, proposed by Wollaston in
1801, developed by de La Rive in 1830, confirmed by Ericson-Auren and Palmaer in
1901, and rediscovered by Whitney in 1903 [8].
As early as 1819, Hall demonstrated the necessity of dissolved oxygen for appreciable
corrosion of iron in water at ordinary temperatures and Sir Humphrey Davy published
results of his work on cathodic protection of copper bottoms for British naval vessels in
1824. These early experiments established a practical base for the application of
cathodic protection which led to the development of galvanized iron.
In 1906, Committee U of the American Society for Testing Materials (ASTM) was
formed to promote the development of corrosion tests. Shortly afterward, other
organizations began to pay attention to corrosion and its control.
Among the pioneers in studying the effects of corrosion was the American Committee on
Electrolysis, which noted in 1921 that its preliminary report had been published in
October, 1916. This committee, composed of representatives of the American Institute
of Electrical Engineers, American Electric Railway Association, American Railway
Engineering Association, National Bureau of Standards, and others, concerned itself
with the then serious problem of stray current damage to underground metal structures,
especially the protection of communication cable from electrified streets and interurban
railways (Figure 1.6 and Figure 1.7).

Figure 1.6. An “electrolysis surveyor” using a McCollum Earth Current Meter
from the early 1920s (Figure courtesy of East Bay Municipal Utility District)


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©2017 by NACE International

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1. Scope and Language of Corrosion

PART II: ENVIRONMENTS

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6. High Temperature Corrosion

PART III: MATERIALS AND HOW THEY CORRODE

9. Failure Analysis and Design Considerations

PART IV: METHODS OF CONTROL

10. Protective Coatings

11. Cathodic Protection

12. Corrosion Inhibitors

PART V: TESTING AND MONITORING

13. Corrosion Testing and Monitoring

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1.1. What is Corrosion?

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A dramatic presentation of corrosion problems was recently published, in which the

1.2. Purpose of this Book

Many become engaged in controlling or preventing corrosion by appointment rather than

Certainly, anyone concerned with corrosion work is primarily interested in control

1.2.1. Economic and Societal Significance

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1. better dissemination of the existing information through education and training,

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1. Lost productivity because of outages, delays, failures, and litigation

1.2.2. Corrosion Around Us

1. The automobile is a veritable corrosion-testing device. Materials must be selected

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1.2.3. Choosing the Right Material

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A surface-layer formation, whether it is oxide, carbonate, sulfate, or any other

1. Moist air is more corrosive than dry air.

1.3. Historical Perspective

Many interesting references and reflections on historical aspects of corrosion can be

Table 1.2. Historical landmarks of discoveries related to the understanding and

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