Water Corrosivity

A major use of water in industry is the transfer of heat and the production of steam. There
is extensive use of cooling water in almost every manufacturing process, in commercial
air conditioning, and even a substantial percentage in domestic air conditioning. Water is
used in the passive sense for potable and for fire control purposes. Fossil and nuclear fuel
steam plants are encountered in the heating and power generating fields.

According to the American Waterworks Association (AWWA) industry database, there is

approximately 1,483,000 km of municipal water piping in the United States. This number
is not exact, since most water utilities do not have complete records of their piping
system. The sewer system consists of approximately 16,400 publicly owned treatment
facilities releasing some 155 million meter cube of wastewater per day (1995). The total
annual direct cost of corrosion for the nation’s drinking water and sewer systems was
estimated at $36.0 billion. This cost was contributed to by the cost of replacing aging
infrastructure, the cost of unaccounted-for water through leaks, the cost of corrosion
inhibitors, the cost of internal mortar linings, and the cost of external coatings and
cathodic protection.

Water can be corrosive to most metals. Pure water, without dissolved gases (e.g., oxygen,
carbon dioxide, and sulfur dioxide) does not cause undue corrosion attack on most metals
and alloys at temperatures up to at least the boiling point of water. Even at temperatures
of about 450oC, almost all of the common structural metals, except magnesium and
aluminum, possess adequate corrosion resistance to high-purity water and steam. In
summary, the factors influencing the corrosion of materials in water systems are:

1. Physical configuration of the system;

2. Chemistry of the water (hardness salts, chlorides, and dissolved gases being the most
important);
3. Presence of solids in the water;
4. Flow rate;
5. Temperature of the water;
6. Presence of bacteria.

Corrosion Cells and Factors Causing Corrosion

Introduction

As described in the previous Chapter, corrosion damage may take various forms which
are themselves triggered by apparently different compounding factors. The initiation and
 progression of corrosion processes indeed depend on the complex interaction of a
multitude of factors such as:

• Nature of the metal or alloy

• Presence of inclusions or other foreign matter at the surface
• Homogeneity of the metallic structure
• Nature of the corrosive environment
• Incidental environmental factors such as variations in the presence of dissolved
oxygen, of temperature, and in the velocity of movement either of the environment
or of the system itself
• Other factors such as stress (residual or applied, steady or cyclic)
• Oxide scales (continuous or broken)
• Presence of deposits on surfaces
• Fayed surfaces and the possibility of corrosion crevices
• Galvanic effects between dissimilar metals
• Occasional presence of stray electrical currents from external sources

The nature of the driving forces behind these factors has been the subject of scientific
studies by many scientists in the early part of the twentieth century. In a landmark paper,
Mears and Brown have summarized 18 mechanisms, listed in the following Table, by
which differences in potential may develop on metal surfaces [1].

Causes of corrosion currents

There is a vast body of information relating practically all the previously listed factors to
actual field observations and subsequent analysis of failed components. These failure
investigations are typically carried out in a detailed mechanistic ‘bottom-up’ manner
whereby a failed component would be sent to the laboratory where analytical techniques
would then be used following well established protocols. Chemical analysis, hardness
testing, metallography, optical and electron microscopy, fractography, X-ray diffraction
and surface analysis are specialized tools used in such investigations.

However, this approach alone provides little or no insight into the real causes of failure.
Underlying causes of serious corrosion damage that can often be cited include human
factors such as lack of corrosion awareness, inadequate training and poor
communication.Further underlying causes may include weak maintenance management
systems, insufficient repairs due to short term profit motives, a poor organizational
‘safety culture’, defective supplier's products, or an incorrect material selection.

It is thus apparent that there can be multiple causes associated with a single corrosion
mechanism. Clearly, a comprehensive failure investigation providing information on the
root cause of failure is much more valuable than one merely establishing the corrosion
mechanism(s).Establishing the real causes of corrosion failures (often related to human
behavior) is a much harder task than merely identifying the failure mechanisms.

In contrast to the traditional scientific mechanistic approach, systems engineers prefer the
‘top-down’ approach that broadens the definition of the system and is more likely to
include causes of corrosion failures such as human behavior.This is consistent with the
lessons to be learned from the UK Hoar Report which stated that corrosion control of
even small components could result in major cost savings because of the effect on
systems rather than just the components

Atmospheric Corrosion

Introduction

Atmospheric corrosion is surely the most visible of all corrosion processes, e.g. rusty
bridges, flag poles, buildings and outdoor monuments. The large segment of the paint
industry committed to the manufacture and application of products for the protection of
metals, as well as the large-scale operations of the galvanizing industry attest to the
importance of controlling atmospheric corrosion. (reference)

Economic losses caused by atmospheric corrosion are tremendous and therefore account
for the disappearance of a significant portion of metal produced. Consider, for instance,
agricultural machinery, steel structures, fences, exposed metals on buildings, automobile
mufflers or bodies, and the myriad of other metal items which are discarded when they
become unusable as a result of corrosion. These constitute direct losses from corrosion.

Atmospheric corrosion has been reported to account for more failures in terms of cost and
tonnage than any other type of material degradation processes. This particular type of
material degradation has recently received more attention, particularly by the aircraft
industry, since the Aloha incident in 1988, when a Boeing 737 lost a major portion of
the upper fuselage in full flight at 7,300 m.

All of the general types of corrosion attack occur in the atmosphere. Since the corroding metal is not
bathed in large quantities of electrolyte, most atmospheric corrosion operates in highly localized
corrosion cells, sometimes producing patterns difficult to explain as in the example of this rusting
galvanized roof.

Rusting galvanized roof with regular bands of rust

Thus, calculation of the electrode potentials on the basis of ion concentration, the
determination of polarization characteristics, and other electrochemical operations are not
as simple in atmospheric corrosion as they are in liquid immersion corrosion. However,
all of the electrochemical factors which are significant in corrosion processes do operate
in the atmosphere.

Types of Corrosive Atmosphere

While atmospheres can be classified into four basic types, most environments are mixed and present no
clear demarcation. Furthermore, the type of atmosphere may vary with the wind pattern, particularly
where corrosive pollutants are present, or with local conditions such as illustrated in the following.

Industrial

An industrial atmosphere is characterized by pollution composed mainly of sulfur

compounds such as sulfur dioxide (SO2), a precursor to acid rain, and nitrogen oxides
(NOx), the backbone of smog in modern cities. Sulfur dioxide from burning coal or other
fossil fuels is picked up by moisture on dust particles as sulfurous acid. This is oxidized
by some catalytic process on the dust particles to sulfuric acid which settles in
microscopic droplets and fall as acid rain on exposed surfaces. The result is that
contaminants in an industrial, atmosphere, plus dew or fog, produce a highly corrosive,
wet, acid film on exposed surfaces.

In addition to the normal industrial atmosphere in or near chemical plants, other corrosive
pollutants may be present. These are usually various forms of chloride which may be
much more corrosive than the acid sulfates. The reactivity of acid chlorides with most
metals is more pronounced than that of other pollutants such as phosphates and nitrates.

Marine

A marine atmosphere is laden with fine particles of sea mist carried by the wind to settle on exposed
surfaces as salt crystals. The quantity of salt deposited can vary greatly with wind velocity and it may, in
extreme weather conditions, even form a very corrosive salt crust, similar to what is experienced on a
regular basis by sea patrolling aircraft or helicopters as shown in the following Figure.

Sea salt deposited on the external surface a) of a Cormorant sea and rescue
helicopter radar antenna, and b) salt causing corrosion to the antenna internal
components due to a broken seal. (courtesy Major S.J.R. Giguère)

The quantity of salt contamination decreases with distance from the ocean, and is greatly affected by
wind currents. The marine atmosphere also includes the space above the sea surfaces where splashing
and heavy sea spray are encountered. The equipment exposed to these splash zones are indeed subjected
to the worst conditions of intermittent immersion with wet and dry cycling of the corrosive agent as
illustrated in the following Figure.

Aircraft carrier top deck. (courtesy Mike Dahlager, Pacific Corrosion Control
Corporation)

Rural

Rural atmospheres are typically the most benign and do not contain strong chemical
contaminants, that is unless one is close to a farm operation where byproducts made of
various waste materials can be extremely corrosive to most construction materials.

Arid or tropical atmospheres are special variations of the rural atmosphere. In arid
climates there is little or no rainfall, but there may be a high relative humidity and
occasional condensation. This situation is encountered along the desert coast of northern
Africa. In the Tropics, in addition to the high average temperature, the daily cycle
includes a high relative humidity, intense sunlight, and long periods of condensation
during the night. In sheltered areas, the wetness from condensation may persist long after
sunrise. Such conditions may produce a highly corrosive environment.

Indoor

Normal indoor atmospheres are generally considered to be quite mild when ambient
humidity and other corrosive components are under control. However, some
combinations of conditions may actually cause relatively severe corrosion problems.
While there is no typical contaminant or set of conditions associated with an indoor
atmosphere, any enclosed space which is not evacuated or filled with a liquid can be
considered an indoor atmosphere. If not ventilated, such an environment may contain
fumes, which in the presence of condensation or high humidity could prove to be highly
corrosive.

Even in the absence of any other corrosive agent, the constant condensation on a cold
metallic surface may cause an environment similar to constant immersion for which a
component may not have been chosen or prepared for. Such systems are commonly
encountered in confined areas close to ground level or, worse, below ground where high
humidity may prevail. The following Figure shows the advanced corrosion of the frame
and contacts in an electric junction box only four years after a building was completed.
While the junction box in this example was only at the ground level, the wires coming to
the box were buried without additional insulation and in constant contact with much
cooler ground than ambient air in the room.

Corrosion Electrochemistry

Introduction

While corrosion can take any one of the several forms, the mechanism of attack in
aqueous environments will involve some aspect of electrochemistry. There will be a flow
of electrons from certain areas of a metal surface to other areas through an
environment capable of conducting ions.

Ulick R. Evans, the British scientist who is considered by many as the "Father of
Corrosion Science", has said that "Corrosion is largely an electrochemical
phenomenon, [which] may be defined as destruction by electrochemical or chemical
agencies...".

Historical Theories on Corrosion by UR Evans

Corrosion in an aqueous environment and in an atmospheric environment is an

electrochemical process because corrosion involves the transfer of electrons between a
metal surface and an aqueous electrolyte solution. It results from the overwhelming
tendency of metals to react electrochemically with oxygen, water, and other substances in
the aqueous environment. In this context, the term anode is used to describe that portion
of the metal surface that is actually corroding while the term cathode is used to describe
the metal surface that consumes the electrons produced by the corrosion reaction.
(reference)
An electrochemical reaction is defined as a chemical reaction involving the transfer of
electrons. It is also a chemical reaction which involves oxidation and reduction. Since
metallic corrosion is almost always an electrochemical process, it is important to
understand the basic nature of electrochemical reactions. The discoveries that gradually
evolved in modern corrosion science have, in fact, played an important role in the
development of a multitude of technologies we are enjoying today. These principles are
illustrated with the use of a Daniell cell in which copper and zinc metals are immersed in
solutions of their respective sulfates. The Daniell cell was the first truly practical and
reliable electric battery that supported many nineteenth century electrical innovations
such as the telegraph.

The fact that corrosion consists of at least one oxidation and one reduction reaction is not
always as obvious as it is in batteries. The two reactions are often combined on a single
piece of metal as illustrated schematically here for a piece of steel and in the following
Figure for a piece of zinc immersed in an acidic solution.

Electrochemical reactions occurring during the

corrosion of zinc in air-free hydrochloric acid

In this Figure, a piece of zinc immersed in hydrochloric

acid solution is undergoing corrosion. At some point on
the surface, zinc is transformed to zinc ions, according
to equation. This reaction produces electrons and these
pass through the solid conducting metal to other sites
on the metal surface where hydrogen ions are reduced
to hydrogen gas according to equation.

These equations illustrate the nature of an electrochemical reaction for zinc. During such
a reaction, electrons are transferred, or, viewing it another way, an oxidation process
occurs together with a reduction process. The overall corrosion processes are summarized
in the following equation:
Briefly then, for corrosion to occur there must be a formation of ions and release of
electrons at an anodic surface where oxidation or deterioration of the metal occurs. There
must be a simultaneous acceptance at the cathodic surface of the electrons generated at
the anode. This acceptance of electrons can take the form of neutralization of positive
hydrogen ions, or the formation of negative ions. The anodic and cathodic reactions must
go on at the same time and at equivalent rates. However, corrosion occurs only at the
areas that serve as anodes.

by Matthew V. Veazey, Staff Writer

An important part of Europe?s rich musical heritage is crumbling away? literally.

Often constructed of lead or lead-tin alloys, the pipes on organs at churches and
other venues throughout Europe are under attack from corrosion. There are more
than 10,000 historical pipe organs in Europe, and some were built more than 500
years ago. An international team of researchers is hopeful that corrosion
inhibitors and surface treatments will help to prolong the life of these
irreplaceable instruments.

?The treatments hitherto used for corroded pipes have been irreversible,? says
Carla Martini, Research Associate with the University of Bologna?s Institute of
Metallurgy (Bologna, Italy). ?New materials with different compositions and
behaviors have been used to repair damaged pipes?sometimes with destructive
results. Or, even worse, irreplaceable historic pipes have been exchanged for
new ones, thereby causing damage to the instrument as a whole, its quality of
sound, and its original characteristics.?

?The ideal protection treatment should be easy to apply by restorers, cost-

effective, reversible, and should not change too much the color of the metal
or?most important?the sound of the pipe,? says Martini. ?We are not developing
a new inhibitor, but we are trying to apply known inhibitors and/or treatments to
[lead or lead-tin pipes].? Aside from the University of Bologna, other research
partners in the European Commission- funded ?Corrosion of Lead and Lead-Tin
Alloys of Organ Pipes in Europe? (COLLAPSE) project include the Göteborg
University?s Göteborg Organ Art Center (GOArt) (Göteborg, Sweden), Chalmers
University of Technology (Göteborg, Sweden), St. Jakobi Church (Lübeck,
Germany), and the organ manufacturer Marcussen & Søn Orgelbyggeri A/S
(Aabenraa, Denmark).

Martini points out that corrosion most often concentrates around the foot of an
organ pipe. The foot is the conical tip of the pipe that is close to the wind inlet. ?
It?s worth noting that this kind of corrosion typically affects the inner side of the
pipe and may not be visible from the outside until the pipe breaks out,? she says.

?The corrosion starts in the lower part of the foot and moves gradually upward in
the pipe toward the mouth area,? adds Carl Johan Bergsten, Research Engineer
with GOArt. ?If nothing is done, there will be cracks and, finally, holes in the pipe
foot wall. The pipe will be silent because the wind will not flow through the pipe
mouth area but will disappear through the holes. The sound is generated in the
mouth area, and the tone quality is extremely sensitive to changes in the mouth
area geometries, edges, and surface structures. It is very serious if the corrosion
reaches the mouth area because the historical sound quality will be lost and the
sounding cultural heritage is forever gone.?

The COLLAPSE project involves many variables from a metallurgical standpoint.

In fact, Martini points out that the pipes in a single organ may have very different
compositions. ?In Italian organbuilding, high-tin alloys or pure tin are used for
pipes in the facade of the organ, whereas pipes behind the facade are mostly
made of high-lead alloys,? she says. ?The content of tin in lead alloys used for
pipes may vary in a wide range, from country to country and from organbuilder to
organbuilder.? Bergsten says that older pipes generally have a higher lead
content, but he adds that materials selection also was influenced by regional
traditions as well as the price and availability of tin. ?The material, and
particularly the metal, represented a major part of the cost for an organ in older
times [today the cost of labor is the most expensive part],? he says. ?Tin was
also much more expensive than lead. In general, the prospect pipes? visible from
the outside?are more tinrich compared to the pipes inside the organ. Tin makes
the pipe look brighter and shinier.?

The research began with an investigation of St. Jakobi Church?s noteworthy

Stellwagen organ, which has pure lead pipes and was built in 1467. Martini,
Bergsten, and their colleagues are studying various other ?reference organs? in
several countries as well. In each country, they are examining one corroded
instrument and one that is not significantly affected by corrosion. However, their
roles in the field studies are unique. University of Bologna team members are
responsible for taking samples from corroded pipes so that they can identify
phase composition and morphology of corrosion products as well as characterize
the material. The Chalmers investigators are analyzing the environments of the
church and the organ wind supply. Researchers from GOArt are documenting
pipe corrosion damage with descriptions and photographs. All field studies will
concentrate on high-lead organ pipes?pipes with a tin content of less than 2
wt%?that appear to be affected by organic acids in the indoor environment.
Martini notes that organbuilders that build new organs still use these alloys to
produce pipes.

?We suspect that a high concentration of organic acids in the organ environment
is a key factor in influencing corrosion, according to the measurements made by
the Department of Environmental Inorganic Chemistry at Chalmers University of
Technology,? says Martini. ?As to the material, we can say that the extent to
which ancient samples are affected by corrosion decreases with increasing tin
content in the alloy?in the range of 0 to 1.5 wt% tin.?

Bergsten points out that high concentrations of acetic acid (CH3COOH)? from
200 to 2,000 ppb?have been measured in the organ wind. ?Wood, especially oak
[common in organs], is known to emit organic acids,? he says. ?In addition,
formic acid [HCOOH] and aldehydes were detected. Laboratory research at
Chalmers has shown that acetic acid in low concentrations is corrosive to lead.
Inorganic air pollutants? for instance, sulfur dioxide [SO2] and nitrogen dioxide
[NO2]?do not seem to be the major causes for the corrosion of organ pipes.?

Despite the COLLAPSE team?s findings to date, Bergsten cautions that it is too
early to definitively explain why the organ pipes are corroding.

?We have found corrosive factors at the reference organs [but] it is important to
also investigate other possible corrosive factors like temperature, humidity,
condensation phenomena inside the pipe, and corrosive emissions from
materials inside and outside the organ,? he says. ?There are also preliminary
results showing that the tin concentration in the alloy is important for the pipe
metal corrosion resistance. Also, combinations of the different possible corrosive
factors above could be the reason for the corrosion.?

Bergsten points out that the most promising conservation strategy at this point is
changing the corrosive environment and cleaning the corroded pipe metal
surface with various products and methods. ?Cleaning the corroded pipe is done
primarily to decrease the rate of corrosion,? he says. ?The objective is therefore
to remove corrosive compounds? salts?from the surface. The insoluble corrosion
products?for instance, lead white?are not to be removed. Cleaning should not
affect the metal itself.? If this approach is not successful, Bergsten predicts that
the team will need to resort to some type of surface coating.