Corrosion Mechanism

Modern corrosion science has its roots in electrochemistry and metallurgy. Electrochemistry
contributes an understanding of the mechanism that is basic to the corrosion of all metallic
objects. Metallurgy provides a knowledge of the characteristics of metals and their alloys as
well as the methods of combining the various metals and working them into the desired
shapes.

The type of corrosion mechanism and its rate of attack depend

on the exact nature of the atmosphere in which the corrosion
takes place. In today's industrial setting, the waste products of
various chemical and manufacturing processes find their ways
into the air and waterways. Many of these substances, often
present only in minute amounts, act as either catalysts or
inhibitors of the corrosion process. The corrosion engineer then
needs to be on the alert for the effects of these contaminants.

Many of the coatings used to prevent or slow corrosion can have specific vulnerabilities that
need to be understood. The first step in preventing material corrosion is understanding its
specific mechanism. The second and often more difficult step is designing a type of
prevention. Some metals produce corrosion products that are insoluble, about the same size
molecularly as the parent metal, and that crystallize in the same type of lattice structure.
These are often able to become attached to the metal surface and form a protective coat
against further corrosion. The patina that forms on copper is an example of this type of
coating.

The existence of anodic and cathodic sites on the surface of a piece of metal implies that
differences in electrical potential are found on the surface. These potential differences have a
number of causes. One important mechanism is oxygen concentration cell corrosion, in which
the oxygen concentration in the electrolyte varies from place to place. An underground pipe
that passes from clay to gravel will have a high oxygen concentration in the gravel region and
almost no oxygen in the impermeable clay. The part of the pipe in contact with the clay
becomes anodic and suffers damage.

A similar situation is found where a pipe passes under a road. The section under the road
(which is the more difficult to get at for repair) is oxygen deprived and will suffer the greatest
damage. The cure for this is cathodic protection, which involves the use of a sacrificial anode
such as zinc or aluminum. In this situation, the metal to be protected is connected electrically
to a piece of scrap metal that will take its place as the anode. The anode is destroyed by the
corrosion reaction, leaving the cathode intact. This technique is still used extensively to
protect underground gas and water pipelines.

Concentration cells may also be formed where there are differences in metal ion
concentration. A copper pipe in contact with copper ion solutions of different concentrations
will corrode at the part in contact with the more dilute solution. This is an obvious problem
when copper pipes are used to carry flowing water. Parts of the copper surface in contact with
the more quickly moving fluid will be more negative and therefore anodic. This phenomenon
plays an important part in the erosion corrosion of copper and its alloys.

Although most metals are crystalline in form, they generally are not continuous single crystals,
but rather are collections of small grains or domains of localized order. Metal objects are
formed from melts in which microcrystals form as the liquid cools and solidifies. In the final
state, these microcrystals have different orientations with respect to one another. The edges
of the domains form grain boundaries, which are an example of planar defects in metals.
These defects are usually sites of chemical reactivity. The boundaries become anodic, while
the grains themselves are the cathodes. The boundaries are also weaknesses, the places where
stress cracking begins.

Perhaps the best known of all corrosion types is galvanic corrosion, which occurs at the
contact point of two metals or alloys with different electrode potentials. An example of this
might be brass detail in contact with copper hot-water pipes. The brass becomes anodic and
suffers the loss of its zinc atoms. Brass in contact with galvanized steel is protected, while the
zinc coating on the steel is first dissolved, leaving the steel open to attack for the same
reason. An obvious area of concern is the use of one type of metal as bolts, screws, and welds
to fuse together pieces of another metal. The combination to be desired is the large anode-
small cathode combination. Bolts, screws, and so on should be made of the metal less likely to
be oxidized so that the bolt or weld is cathodically protected.

Similar electrical potentials may also be developed between two areas of a component made
of a single metal as a result of small differences in composition or structure or of differences
in the conditions to which the metal surface is exposed. That part of a metal component
which becomes the corroding area is called the "anode"; that which acts as the other plate of
the battery is called the "cathode" and does not corrode, but is an essential part of the
system. In the corrosion systems commonly involved in buildings there may often be only a
single metal involved, with water containing some salts in solution as the electrolyte.
Corrosion may even take place with pure water, provided that oxygen is present. In such cases
oxygen combines with the hydrogen generated at the cathode, removing it and permitting the
reaction to go on.

Other agents, notably certain bacteria in the soil which remove hydrogen, can also act as
depolarizing agents and thus promote the corrosion reaction. Steel, because of its low cost
together with its many desirable properties, is the most common metal used in buildings. It
can often be protected adequately by the application of suitable coatings. For certain
purposes other metals more resistant to corrosion may be a better choice, depending on initial
cost and expected service life. Metal components used in buildings can be grouped for
purposes of discussing corrosion into four general categories: 1) those used on the exterior as
cladding, roofing and flashings, 2) those incorporated in the construction as structural and
reinforcing steel, masonry ties and damp courses, 3) those used in the services to a building as
piping, storage tanks for hot water, drains and heating ducts, 4) those buried in the ground.

Of great importance is the conductivity of the corroding solution. When large areas of the
surface are in contact with a water solution of high conductivity, such as seawater, the attack
on the anodic metal may spread far from its contact point with the cathodic metal. This is a
less severe situation than that which occurs in soft water or under atmospheric conditions in
which the attack is localized in the vicinity of the contact. In the absence of dissolved oxygen
or hydrogen ions to maintain the cathode process, galvanic corrosion does not occur. It is
possible to combine different metals such as copper and steel in closed hot-water systems
with little corrosion.

Other preventive measures involve the use of protective coatings and modification of the
environment. Some trace impurities can significantly reduce the rate of corrosion and can be
added in low concentration to the surrounding medium. Paint is the most common coating
used to slow the rate of atmospheric corrosion. Many other materials, such as plastics,
ceramics, rubbers, and even electroplated metals, can be used as protective coatings. The
corrosion resistance of a metal can be greatly increased by the proper choice of alloys. For
example, aluminum added to brass will increase its corrosion resistance.
Testing for Localized Corrosion
These are the types of corrosion in which there is intense attack at localized sites on the surface of a
component whilst the rest of the surface is corroding at a much lower rate - either because of an
inherent property of the component material (such as the formation of a protective oxide film) or
because of some environmental effect. Indeed the main surface may be essentially under satisfactory
corrosion control. In such circumstances, if corrosion protection breaks down locally then corrosion may
be initiated at these local sites.

If this event occurs under a deposit on the surface (perhaps a weld deposit or some solid debris from the
environment) or at the joint of a bolted assembly etc, the attack is termed, “crevice corrosion”. If the
attack initiates on the free surface of a component, it is termed “pitting”. The resistance to these two
types of localized corrosion varies greatly between different materials and is extremely dependent upon
environmental factors.

The occurrence of localized corrosion is a manifest proof that the anodic surface area can be much
smaller than the cathodic. The Sa/Sc ratio, or degree of localization, can be an important driving force
of all localized corrosion problems since a corrosion situation corresponds to equal anodic and cathodic
absolutes currents. Corrosive microenvironments, which tend to be very different from the bulk
environment, often play a role in the initiation and propagation of corrosion pits. This greatly
complicates the prediction task.

In general terms, small corrosion anodic areas correspond to severe corrosion problems with low
detectability. The industrial importance of localized corrosion problems has been revealed in many
reports. The following pie chart summarizes the findings of 363 corrosion failure cases investigated in a
major chemical processing company [1]. The importance of pitting comes second (22%) after general
corrosion and before stress corrosion cracking (SCC) which is, by the way, often initiated by pitting.
Crevice corrosion comes fourth at 12%.

Information Module
Autocatalytic process - Stage one

Stage one of a crevice formation

At time zero, the oxygen content in the water occupying a crevice is equal to the level of
soluble oxygen and is the same everywhere.

Calculation example

Assuming the total surface area is 100 cm2

Assuming the current density is 22 µA cm-2 for both the anodic and cathodic reactions
(see corrosion theory and mixed potential diagram for more details)

The total anodic current (corrosion reaction) of 2.2 mA is absolutely equal to the total
cathodic current while the corrosion penetration rate is related to 22 µA cm-2
corresponding to 0.255 mm y-1 or 10 mpy for a steel specimen.

For all intent and purpose such a corrosion rate is considered benign for most
applications.

Back Forward
Autocatalytic process - Stage two

Stage two of a crevice formation

Because of the difficult access caused by the crevice geometry, oxygen consumed by normal
uniform corrosion is very soon depleted in the crevice. The corrosion reactions now specialize
in the crevice (anodic) and on the open surface (cathodic). The large cathodic surface (Sc) vs.
anodic surface (Sa) ratio (Sc/Sa) that forms in these conditions is a definitive aggravating factor
of the anodic (corrosion) reaction.

Calculation example

Assuming the total surface area is still 100 cm2 with 99 cm2 occupied by the cathodic
area and only 1 cm2 corresponding to the crevice or anodic surface. In reality this
imbalance can be larger or smaller depending on local geometry characteristics.

The surface area ratio would then be 99/1 or 99.

Assuming the initial current density of 22 µA cm-2 is the same for the cathodic reaction
this would mean that the total cathodic current would be equal to 99 cm2 x 22 µA cm-2
or 2.18 mA.

This also mean that the corrosion or anodic reaction has to provide the electrons to
satisfy the cathodic demand (see corrosion theory and mixed potential diagram for
more details)

The total anodic current would therefore now be 2.18 mA and the anodic current
density be 2.18 mA/1cm2 or 2.18 mA cm-2.
The chronology of a Crevice - Stage three

Stage three of a crevice formation

In stage three of the crevice development a few more accelerating factors fully develop:

The metal ions produced by the anodic corrosion reaction readily hydrolyze giving off
protons (acid) and forming corrosion products. The pH in a crevice can reach very acidic
values, sometimes equivalent to pure acids.
The acidification of the local environment can produce a serious increase in the
corrosion rate of most metals. See, for example, how the corrosion of steel is affected
as a function of water pH.
The corrosion products seal even further the crevice environment.
The accumulation of positive charge in the crevice becomes a strong attractor to
negative ions in the environment, such as chlorides and sulfates, that can be corrosive
in their own right.

Back
Material Factor in Corrosion Failure

The material factor controlling the probability of a corrosion failure

The choice of a material is the result of several compromises. For example, the technical
appraisal of an alloy will generally be a compromise between corrosion resistance and some
other properties such as strength and weldability. And the final selection will be a compromise
between technical competence and economic factors. In specifying a material, the task
usually requires three stages:

Listing the requirements

Selecting and evaluating the candidate materials
Choosing the most economical material.

The materials selection process is also influenced by the fact that the materials are either
considered for the construction of a new system, or for the modification or repairs in an
existing facility. For the construction of new equipment, the selection procedure should begin
as soon as possible and before the design is finalized. The optimum design for corrosion
resistance will often vary with the material used.

In a repair application, there is usually less opportunity for redesign, and the principal
decision factors will be centered on delivery time and ease of fabrication in the field. It is also
advisable to estimate the remaining life of the equipment so that the repair is not over-
designed in terms of the corrosion allowance.
Corrosion Allowance
Corrosion allowance is the tribute to corrosion damage paid by designers to compensate for
the inevitable effects of corrosion on a structure exposed to environments. With the advents
of new corrosion prevention measures and improvements in corrosion monitoring technologies,
there are always some questions to revisit the allowances made to corrosion damage. You can
find here what some experts think of this situation.

Find more on corrosion allowance ... and monitoring

... and design

... and repairs

Environment Factor in Corrosion Failure

The environment factor controlling the probability of a corrosion failure

According to the basic materials degradation model, the principal features underlying the
environment factor consist in a long list of elements describing the chemical makeup of the
environment as well as the aggravating contributors that can be part of operating conditions
as schematically illustrated.

A testing program that would investigate only the nominal condition without consideration for
effects such as flow, pH cells, deposits, and other galvanic effects is useless for lifetime
prediction. An exact and complete environmental definition must include a description of the
microenvironment actually in contact with a metallic surface. However, the circumstances
producing this microenvironment are also important. Processes such as wetting and drying,
build-up of deposits, and changes in flow patterns greatly influence the chemistry of a
surface.
Tank Corrosion Design
Tank bottoms

Six common tank bottom arrangements are illustrated here with comments from a corrosion
engineering point of view. (Internet reference)

Worst - The square corner flat bottom arrangement invites early

failure from the inside at the corner weld where sediment will
collect, increasing the probability of crevice attack. Moisture
penetrating the flat bottom to pad support invites rapid crevice
corrosion from the underside.

Good corners, poor outside - The rounded bottom shown here is

much more resistant from the inside, but is actually worse from the
outside as condensation is funnelled directly into the crevice
between the tank bottom and pad support.

Poor inside, poor outside - The grout used here to divert such
condensation does help initially but soon shrinks back and becomes
a maintenance demand itself.

Good inside, good outside - The drip skirt shown here is much the
best arrangement for flat bottom tanks.

Good inside, good outside, fatigue resistant - The concave bottom

shown here and the dished head bottom on supports below are very
good and superior to all flat bottom tanks not only in corrosion
resistance but also in fatigue. Fatigue stresses from filling and
emptying are seldom considered in design, but can be significant
and have led to failures in flat bottom tanks. The concave and
dished head arrangements can withstand much greater fatigue
loadings than can flat bottoms.

Best inside, best outside, fatigue resistant - Dished head bottom.

Tank bottom outlets

Water left standing in the bottom of stainless steel tanks has been a source of tank bottom
failures in both fresh and saline waters.

Side outlets and centre outlets, shown in here and below, allow for
convenient construction but invite early failure of tank bottoms. Not
only is a layer of stagnant water held on the tank bottom but
sediment cannot be easily flushed out - poor designs.

A flush side outlet and a recessed bottom outlet as shown here and
below allow the bottom to be completely drained and all debris and
sediment to be flushed out, leaving the bottom clean and dry - good
designs.

The sloped arrangements shown in here and below make it easier to

flush out and clean- best designs.

Bottom corner welds

Poor inside, worst outside - When the side wall forms a right
angle with the bottom, the fillet weld is seldom as smooth as
shown here. It is usually rough and frequently varies in width
compensating for variations in fit up. Because of the
location, it is very difficult to grind and blend the weld into
the adjacent sides. Debris tends to collect and is difficult to
remove, leading to under sediment type crevice attack.
Poor inside, good outside - Unless welded from the outside
as shown here, the crevice is vulnerable to crevice attack.

Best inside, good outside, fatigue resistant - Rounding the

corner and moving the weld to the side wall overcomes both
short comings as shown in Figure 14 15. This construction has
much improved corrosion resistance and also has better
fatigue resistance. (Internet reference)
Corrosion Design of Structural Elements
(Internet reference)

All attachments create potential crevice sites. The figure on the

right shows a tray support angle with intermittent welds adequate
for strength. There is a severe crevice between the angle and the
inside wall of the vessel which will become filled with debris and
invite premature failure from crevice corrosion. Adequate support,
severe crevice

This figure shows the same tray support with a continuous seal weld
at the top preventing unwanted material from finding its way down
the wall and into the crevice is still open from the bottom but this is
a much less severe crevice which severe crevice vapors but not
material can still enter. Good crevice resistance

And here is a full seal weld at the top and bottom of the tray
support angle. Here the crevice is fully sealed. Best crevice
resistance

The figure on the right shows a reinforcing pad to which other

attachments are frequently welded. The intermittent weld creates a
severe pad to sidewall crevice inviting premature failure. Adequate
strength

It takes very little more time to complete the seal weld as shown
here, which should always be done. It is good practice to drill a
weep hole through the outer wall and must be done if the vessel is
to receive a stress relief or solution anneal, otherwise the expansion
of the trapped air could damage the vessel wall. Best crevice
resistance
The figure on the right shows structural angles positioned so they
can drain, an important factor when shutting down and flushing out.

Angles should never be positioned as in the top section as shown

here. The best position for complete drainage is shown in the lower
view.

When channels are used, drain holes

should be drilled about every 12 in. (300
mm) in the centre, unless they can be
positioned as in the right hand view of
the figure shown here.

Continuous fillet welds on support

beams will seal the severe beam to
horizontal plate crevice shown in the
upper section of the figure shown here.

Baffles in tanks and heat exchangers create dead spaces where

sediment can collect and where full cleaning is difficult. The figure
on the right shows a cut out at the lower corner of a tank baffle.
Good

The figure here shows a cut out in the lower portion of a heat
exchanger tube support plate. Both this arrangement and the one
above reduce debris collection and facilitate cleaning. Good

(Internet reference)
Corrosion Design of Heaters and Inlets
(Internet reference)

Heaters should be located so the do not

cause hot spots on the vessel wall. In
this figure, the poor location of heaters
creates hot spots which in turn may
result in higher corrosion in the area
between the heater and vessel wall.
The good design avoids hot spots by
centrally locating the heater.

When a concentrated solution is added

to a vessel, it should not be introduced
at the side as shown here in the poor
design. Side introduction causes
concentration and uneven mixing at the
side wall. With the good design, mixing
takes place away from the side wall. It
is also good design practice to
introduce feed below the liquid level to
avoid splashing and drying above the
liquid line.
Corrosion Design of Pipe Welds
(Internet reference)

It is frequently convenient to socket weld small diameter stainless

steel pipe rather than butt weld, as shown here. On larger diameter
pipe, over 2 in. (50 mm), a backing ring as shown below is often
used. Both designs may be satisfactory for those services where the
stainless steel alloy has adequate crevice corrosion resistance.

Because of the crevice formed, these designs often lead to

unnecessary corrosion in aggressive environments and are not
recommended. The backing ring has the further disadvantage of
protruding into the flow stream, which in turn can cause product
build up or unnecessary turbulence.

Very often stainless steel piping is installed as commercial quality,

that is without imposing code standards such as the ASME or the
American Petroleum Institute, API, which require full penetration
butt welds. When procurement does not require full penetration
smooth ID butt welds, it is all too common to have a beautiful
looking weld from the outside but incomplete penetration on the
inside, such as shown here.

Many corrosion failures originate in

crevices created by incomplete
penetration at the root of pipe butt
welds. Since ASTM does not cover
fabrication, procurement specifications
must specify full penetration and
smooth ID for the root bead of butt
welds when the weld quality is not
covered by other specifications. The
preferred pipe butt welding procedure
to insure high quality root welds is the
use of GTAW for the root pass with an
inert gas backing. In manual root pass
welds, the hand fed filler metal
technique or the use of consumable
inserts is commonly used. The figure
shown here illustrates some standard
consumable insert designs. Properly
made welds with either technique can
provide a crevice free ID surface with
minimum bead convexity or concavity.

The hand fed filler metal method is more widely used in the chemical process industry but the
experience of the particular company or welders, strongly influences the selection. It is
important that the root bead have adequate and uniform amounts of filler metal melted into
the weld for best corrosion resistance. This addition is readily obtained with consumable
inserts or by skilled welders using the hand fed filler metal method.

There are a number of automatic GTAW machines available for root pass and fill welding. The
root pass can be made using an insert, with automatic wire feed or in thin wall pipe, single
pass welds can be made without filler metal addition. The ID root contour of automatic welds
is very consistent and it is an excellent process to use where the economics are favorable.
Automatic GTAW is a particular advantage for tubing and pipe 2 in. (50 mm) diameter and
less. Three good pipe to flange welding arrangements are shown in the following three figures.

The recessed arrangement shown left avoids the need for machining
or grinding smooth the surface of the weld on the flange face shown
below. Both these arrangements are suitable when the flange is of
the same material as the pipe.

However, neither arrangement is suitable when carbon steel or

ductile iron flanges are used on stainless steel pipe.

In this case a stub end arrangement shown right is preferred. In the

case of pressure piping, the flange design must also be in accordance
with the applicable design or fabrication specification.

For piping and heat exchanger tubing to drain completely necessary to slope the piping or heat
exchanger just enough so that water, will drain and not be trapped where the pipe or tubing
sags slightly between support points. The following figure shows how a water film tends to
remain in horizontal runs of pipe or tubing and how water drains when sloped.

A. Horizontal (standard) - poor design

B. Horizontal sloped - very good design

Rusty Oil Pan

This rusting oil pan should collect oil spillage from the oil reservoir above it. The rain water
collection is thus a necessity by design. However, it is pretty obvious that there is a problem
here. What would you recommend in this particular case? We will post, with your permission,
any solution you can propose to solve this particular problem, if they make good engineering
sense. Please send your answers or solutions to our Educator.

Bruce Hostetler's solution

Corrosion and Design

Naval Materials Click here to enter

Good Corrosion Design?
The photo shows an oil reservoir sitting in an open pan that collects rainwater, which I assume
overflows and takes any collected oil with it. I see three ways of dealing with the rainwater
problem:

1. Locate the oil reservoir within another reservoir with a common cover to keep the
rainwater out altogether;

2. Cover the collection pan to protect it from rainwater, or at least divert it elsewhere;

3. Fashion a depression into the bottom of the collection pan, put a tube up through the
bottom, and place a ball on top of the tube. The ball needs a porous cage around it to
keep it aligned with the top of the tube. The ball needs to be of the proper buoyancy to
float on water, but sink when in oil. The ball will float to let water drain out the bottom
of the tube, and drop back down to seal the tube when most of the water is drained
away.

I like the third idea the best, but then again I always was a fan of Rube Goldberg.

Bruce R Hostetler

What you think of Bruce's solutions? Please send your comments to our Educator.
 Hot Corrosion

Naval Materials Click here to enter

Atmospheric Corrosion Mechanism
Atmospheric corrosion is an electrochemical process, requiring the presence of an electrolyte.
Thin film "invisible" electrolytes tend to form on metallic surfaces under atmospheric corrosion
conditions, when a certain critical humidity level is reached. For iron, this level is around 60%,
in unpolluted atmospheres. The critical humidity level is not a constant - it depends on the
corroding material, the hygroscopic nature of corrosion products and surface deposits and the
presence of atmospheric pollutants.

In the presence of thin film electrolytes, atmospheric corrosion proceeds by balancing anodic
and cathodic reactions. The anodic oxidation reaction involves the dissolution of the metal in
the electrolyte, while the cathodic reaction is often assumed to be the oxygen reduction
reaction. Oxygen from the atmosphere is readily supplied to the electrolyte, under thin film
corrosion conditions.
Exposure Testing
There are many factors to consider when selecting a weathering test station to conduct a test
program. These can be summarized into two categories:

Location: An ideal test site should be located in a clean pollution free area, if pollution
is not deemed to be a parameter, within the geo-climatic region to be used. This is
important for the prevention of unnatural effects on the specimens. Within the local
area chosen, there must be no isolated sources of pollution or deleterious atmospheric
contamination.
Maintenance: The exposure maintenance program followed by the test site will also
play a major role in determining the accuracy of testing. It is important for the
specimens on the test racks to be correctly maintained. This involves ensuring the
correct mounting method, and constant follow-up attention to maintain the quality.

For direct exposure the specimen is mounted on the exposure frame open backed or solid
backed, and subject to all atmospheric effects. This type can be used at a number of exposure
angles. The standard angles used are 45, 5, and 90 degrees, these angles being referenced
from a horizontal angle of 0 degree. The angle chosen should be one that matches as closely
as possible the position of the end use of the material. The racks should be cleaned on a
regular basis to remove mildew and algae if these contaminate producers are present on the
test site.

To see a picture of the rural marine atmosphere exposure rack at Dockyard Laboratory
(Pacific), 'click here'.
Direct exposure testing rack

Rural marine atmosphere exposure rack at Dockyard Laboratory (Pacific). Photo courtesy of
Defence Research Establishment Atlantic.
Microenvironments
The corrosivity due to atmospheric conditions can be greatly affected by local conditions such
as wind speed and direction, dust, debris, humidity, condensation and electrolytic species.
These local conditions can change greatly within a few meters, depending on patterns in air
turbulence. One extreme example of local variations due to the corrosivity of a seawater
environment is the top deck of an aircraft carrier, where waves and seawater mist are
abundant.

An example of local seasonal differences often exist in countries where deicing salts are used
in the winter months. The following results have been obtained by exposing CLIMAT coupons in
the vicinity of two important highways in Eastern Ontario. The transport and deposition of
aerosols are subject to mass transport laws such as convection and turbulent diffusion. Based
on these principles, the pattern of aerosol surface deposition can be modeled near obstacles.
In such a modeling experiment, it was found that aerosol deposition rates onto and near an
obstacle have a very localized structure due to variations in wind speed, wind speed gradients
and turbulence.
Corrosion by Natural Waters
Abundant supplies of fresh water are essential to industrial development. Enormous quantities
are required for cooling of products and equipment, for process needs, for boiler feed and for
sanitary and potable water. It was estimated, in 1980, that the water requirements for
industry in the USA approximated 525 billion liters per day. A substantial quantity of this water
was reused. The intake of "new" water was estimated to be about 140 billion liters daily. If this
water was pure and contained no contaminants, there would be little need for water
conditioning or water treatment.

The fast-growing demand for clean, fresh water coupled with the need to protect and enhance
the environment, has made many areas of the world vulnerable to water shortages for various
human uses. As they interact with the electricity industry, these uses encompass agricultural
irrigation, thermoelectric generation, municipal water and wastewater treatment and
distribution, and industrial processes. The dependence of electricity supply and demand on
water availability can impede the sustainability of economic growth, adversely affect future
growth in electricity demand, cause shortages in current supplies of electricity, and have
direct impact on power system planning and expansion.

Water possesses several unique properties, one being its ability to dissolve to some degree
every substance occurring on the earth's crust and in the atmosphere. Because of this solvent
property, water typically contains a variety of impurities. These impurities are a source of
potential trouble through deposition of the impurities in water lines, boiler tubes and on
products which are contacted by it.

Dissolved oxygen, the principal gas present in water, is responsible for costly replacement of
piping and equipment by corrosive attack on metals with which it comes in contact. The origin
of all water supply is moisture that has been evaporated from land masses and oceans and
subsequently precipitated from the atmosphere. Depending on weather conditions, this may
fall in the form of rain, snow, sleet or hail. As it falls, this precipitation contacts gases
comprising the atmosphere and suspended particulates in the form of dust, industrial smoke
and fumes, and volcanic dust and gases. (Handbook) (Internet references)

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

approximately 1,483,000 km (876,000 mi) 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 m3 (41 billion gallons) 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. (Cost reference)

Information Module

Water constituents
Scaling
Pollutants
Chlorination
Corrosion Costs and Preventive Strategies Study
Download the whole report (Internet reference 26)

The two methods used in this study to estimate the cost of corrosion to the United States are
based on: (1) the cost of corrosion control methods and services, and (2) corrosion costs of
specific industry sectors. Past studies have indicated that the second method is more likely to
incorporate the majority of the major corrosion-related costs and the first method is likely to
miss the significant cost of corrosion management, the cost for direct services related to the
owner/operator, and the cost of loss of capital due to corrosion.

Method 1 – Corrosion Control Methods and Services

With this method, the annual direct cost of corrosion was estimated by adding the cost of
corrosion control methods and services. The corrosion control methods that were considered
include protective organic and metallic coatings, corrosion-resistant alloys, corrosion
inhibitors, polymers, anodes, cathodic protection, and corrosion control and monitoring
equipment.

Other contributors to the total annual direct cost that were reviewed in this report are
contract services (i.e., non-owner/operator services), corrosion research and development,
and education and training.

Method 2 – Industry Sector Analysis

In this study, the U.S. economy was divided into five sector categories and 26 sectors, as
follows:

Infrastructure:
Highway Bridges

Gas and Liquid Transmission Pipelines

Waterways and Ports

Hazardous Materials Storage

Airports

Railroads

Utilities:
Gas Distribution

Drinking Water and Sewer Systems

Electrical Utilities

Telecommunications
 Transportation:
Motor Vehicles

Ships

Aircraft

Railroad Cars

Hazardous Materials Transport

Production and Manufacturing:

Oil and Gas Exploration and Production

Mining

Petroleum Refining

Chemical, Petrochemical, and Pharmaceutical

Pulp and Paper

Agricultural

Food Processing

Electronics

Home Appliances

Government:
Defense

Nuclear Waste Storage

The cost of corrosion was estimated for each of the above categories. When summed, the total
annual cost of corrosion for the industry sectors examined was $137.9 billion. Not all industries
were examined in this study; therefore, the total economic impact on the U.S. economy would
naturally be greater than the $137.9 billion given here.

Download the whole report (776 pages) or one its many appendices
(Internet reference 26)
Materials Cost
Economics enter into every business decision. But, the important criteria should not be the
initial cost of a material, but its life-cycle cost or cost effectiveness. It usually is much more
cost effective to specify a material that will provide an extended life, particularly in areas
that are difficult to repair or in components that would cause major shut-downs in case of
failure. The following two extreme alternatives describe the consideration given to economic
factors when selecting materials for specific service:

A low initial cost system largely based on carbon steel and cast iron which will require
considerable maintenance over the life of the plant. Such a system is a reasonable
choice in areas where labor costs are low and material is readily available
A system based mainly on alloy materials which, if correctly designed and fabricated,
will require minimum maintenance and will function reliably. Rising labor costs in most
industries, together with the need for high reliability in capital intensive plant has
produced a trend to this type of system.

In practice many systems are a mixture of these extreme options resulting in the high initial
costs of one and the high maintenance costs of the other.

Corrosion Costs and Preventive Strategies Study

Corrosion-resistant alloys are used where corrosive conditions prohibit the use of carbon steels
and protective coatings provide insufficient protection or are economically not feasible.
Examples of these alloys include stainless steels, nickel-base alloys, and titanium alloys.
According to U.S. Census Bureau statistics, a total of 2.5 million metric tons of raw stainless
steel was sold in the United States in 1997. With an estimated cost of $2.20 per kg ($1 per lb)
for raw stainless steel, a total annual (1997) production cost of $5.5 billion was estimated. It is
assumed that all production is for U.S. domestic consumption. The total consumption of
stainless steel also includes imports, which account for more than 25 percent of the U.S.
market. Thus, the total consumption of stainless steel can be estimated at $7.3 billion.

Where environments become particularly severe, nickel-base and titanium alloys are used.
Nickel-base alloys are used extensively in the oil production and refinery and chemical process
industries, where conditions are aggressive. Furthermore, there is an increased use of these
alloys in other industries, where high temperature and/or corrosive conditions exist. With the
average price for nickel-base alloys at $13 per kg in 1998, the total sales value in the United
States was estimated at $285 million.

The primary use of titanium alloys is in the aerospace and military industry, where the high
strength-to-weight ratio and resistance to high temperatures are properties of interest.
However, titanium and its alloys are also corrosion-resistant in many environments, and have
therefore found application in oil production and refinery, chemical process, and pulp and
paper industries. In 1998, it was estimated that 65 percent of the titanium mill products were
used for aerospace and 35 percent for non-aerospace applications. The total annual
consumption cost for titanium and titanium alloys for corrosion control applications is
estimated at $150 million.

The total 1998 consumption cost of the corrosion-resistant metals and alloys is estimated at
$7.7 billion. (Internet reference)
Availability of Materials
Materials engineers and purchasing agents become frustrated in trying to obtain materials that
have a limited number of producers or a limited production volume. Such frustration can be
particularly high when a small amount of material is needed to finish a job or replace a failed
piece. Prior to the original specification of a material, consideration should be given to its
future availability for repairs or replacement in the form or forms that it will be used. In those
cases where it might not be available, alternative replacement materials should be identified.

Industry Dynamics: Metals companies are undergoing what can only be described as
wrenching change. The competitive landscape is dramatically changing thanks to the
following drivers: (reference)
Industry consolidation
Globalization
Over capacity
Price erosion
Best Practices: The industry leaders are turning challenges into competitive advantage
and seeking areas where technology can deliver needed improvements.
Managing more complex supply chains: More complex supply chains are emerging as a
consequence of the industry consolidation. Opportunities to benefit include: lower
costs, faster response to customers, flexible product sourcing and more efficient
distribution strategies.
Consolidating disparate systems: Metals companies have built sophisticated
information systems to support their operations. The undeniable strengths of the
existing infrastructure can be leveraged while reining in costs and complexity. New
business models that make decisions about customers and suppliers simple and as
effective are now possible.
Expediting order processing: Understanding customer needs while managing
metallurgical and mill capabilities reduces overall processing time, a key element
toward gaining market share.
Innovative business processes: Redefining supply chain networks to maximize
efficiency and adopting new business processes such as build-to-stock / finish-to-order
allows metals companies to achieve extremely competitive lead times.
Consolidating MRO spending: As an asset-intensive industry, keeping expensive
facilities running is critical. Addressing the challenge of maximizing equipment uptime
while reducing parts inventory uncover major benefits.
Extended value chain: All too often, efficiency stops at the edges of the company.
Streamlining cross-enterprise processes is the next great frontier for reducing costs,
speeding operations and deliveries to create value for customers and shareholders.
Corrosion Monitoring Basics
Naval Materials Web pages related to corrosion monitoring

Corrosion can lead to failures in plant infrastructure and machines which are usually costly to
repair, costly in terms of lost or contaminated product, in terms of environmental damage,
and ultimately it may be costly in terms of human safety. Correct and effective corrosion
monitoring strategies should be used as a proactive tool to assist with operating a plant more
effectively, thereby prolonging its life and gaining optimum throughput. It also enables
continuous monitoring of actual corrosion rates, allowing for timely preventative action if a
variance is observed.

Corrosion monitoring systems vary significantly in complexity, from simple coupon exposures
or hand held data loggers to fully integrated plant process surveillance units with remote data
access and data management capabilities. Experience has shown that the potential cost
savings resulting from the implementation of corrosion monitoring programs generally increase
with the sophistication level (and cost) of the monitoring system. Corrosion monitoring is more
complex than the monitoring of most other process parameters because:

There are a number of different types of corrosion

Corrosion may be uniform over an area or concentrated in very small areas
(pitting)
General corrosion rates may vary substantially, even over relatively short
distances
There is no single measurement technique that will detect all of these various
conditions

It is therefore helpful to have previous history or even a rough estimate of the types of
corrosion problems to be investigated. It is also advisable to use several complementary
techniques rather than rely on a single monitoring method.

See also:

Data integration
Need for corrosion monitoring
New techniques
Traditional techniques
Selecting points

Many pages of the Naval Materials site discuss specific issues related to corrosion monitoring.
The following links will bring you to some of these pages:

Anodic protection: 1, 2, 3, 4, 5, 6
Atmospheric: 1, 2, 3, 4, 5, 6
Coatings: 1, 2, 3, 4, 5, 6
Concrete: 1, 2, 3, 4, 5, 6
Corrosion allowance: 1, 2, 3, 4, 5, 6
Electrochemical methods: 1, 2, 3, 4, 5, 6, 7, 8, 9, 10
Erosion corrosion: 1, 2, 3, 4, 5, 6
 Gas scrubber: 1, 2, 3, 4, 5, 6
Condition monitoring: 1, 2, 3, 4, 5, 6
Inhibitors: 1, 2, 3, 4, 5, 6
Inspection: 1, 2, 3, 4, 5, 6
Microbial activity: 1, 2, 3, 4, 5, 6
Steel: 1, 2, 3, 4, 5, 6
Techniques: 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13
Under insulation: 1, 2, 3, 4, 5, 6

Information Module

Need for corrosion monitoring

Corrosion monitoring techniques
Selecting points
Data integration

Back to Naval Materials

Corrosion Monitoring Techniques
Corrosion monitoring is the practice of measuring the corrosivity of process stream conditions
by the use of "probes" which are inserted into the process stream and which are continuously
exposed to the process stream condition. Corrosion monitoring "probes" can be mechanical,
electrical, or electrochemical devices.

These probes are an essential element of all corrosion monitoring systems. The nature of the
sensors depends on the various individual techniques used for monitoring but often a corrosion
sensor can be viewed as an instrumented coupon. In older systems, electronic sensor leads
were usually employed for these purposes and to relay the sensor signals to a signal-processing
unit. Advances in microelectronics are facilitating sensor signal conditioning and processing by
microchips, which can essentially be considered to be integral to the sensor units.

Some corrosion measurement techniques can be used on-line, constantly exposed to the
process stream, while others provide off-line measurement, such as that determined in a
laboratory analysis. Some techniques give a direct measure of metal loss or corrosion rate,
while others are used to infer that a corrosive environment may exist.

Real-time corrosion measurements refer to highly sensitive measurements, with a signal

response taking place essentially instantaneously as the corrosion rate changes. Numerous real-
time corrosion monitoring programs in diverse branches of industry have revealed that the
severity of corrosion damage is rarely uniform with time. Complementary data from other
relevant sources such as process parameter logging and inspection reports can be acquired
together with the data from corrosion sensors, for use as input to the management
information system. (Internet reference)

Direct techniques

Corrosion Coupons (intrusive)

Electrical Resistance (ER) (intrusive)
Inductive Resistance Probes (intrusive)
Linear Polarization Resistance (LPR) (intrusive)
Electrochemical Impedance Spectroscopy (EIS) (intrusive)
Harmonic Analysis (intrusive)
Electrochemical Noise (EN) (intrusive)
Zero Resistance Ammetry (ZRA) (intrusive)
Potentiodynamic Polarization (intrusive)
Thin Layer Activation (TLA) and Gamma Radiography (intrusive or non-intrusive)
Electrical Field Signature Method (EFSM) (non-intrusive)
Acoustic Emission (AE) (non-intrusive)
Indirect techniques

Corrosion Potential (non-intrusive)

Hydrogen Monitoring (non-intrusive)
Chemical Analyses
Corrosion Coupons for Corrosion Monitoring
The simplest, and longest-established, method of estimating corrosion losses in plant and
equipment is weight loss analysis. A weighed sample (coupon) of the metal or alloy under
consideration is introduced into the process, and later removed after a reasonable time
interval. The coupon is then cleaned of all corrosion product and is reweighed. The weight loss
is converted to a total thickness loss, or average corrosion rate using proper conversion
equations.

Weight loss determination has a number of attractive features that account for its sustained
popularity. It is:

Simple: No sophisticated instrumentation is required to obtain a result.

Direct: A direct measurement is obtained, with no theoretical assumptions or
approximations.
Versatile: It is applicable to all corrosive environments, and gives information on all
forms of corrosion.

The choice of technique for initial preparation of the coupon surface, and for cleaning the
coupon after use, is critical in obtaining useful data. Both the relevance and reproducibility of
weight loss data are highly sensitive to the inherent suitability of these techniques, and to the
care with which they are executed.

Surface finishing methods vary across a broad range for specific applications. Blasting with
glass bead, sand, or other aggregate can provide an acceptable finish for some applications.
Sanding with abrasive belts, or surface or double disc grinding with abrasive stones also
provides an excellent surface for evaluation. Cleaning of specimens before weighing and
exposure is critical to remove any contaminants that could affect test results.

Reference should therefore be made to NACE Recommended Practice RP-0775 and ASTM G-1 G-
4 for further detail on surface finishing and cleaning of weight-loss coupons.

See also:

Electrical Resistance (ER)

Inductive Resistance Probes
Linear Polarization Resistance (LPR)
Electrical Resistance (ER) for Corrosion Monitoring
The electrical resistance technique is one of the most widely used methods for measuring
material loss occurring in the interior of plant and pipelines. This technique operates by
measuring the change in electrical resistance of a metallic element immersed in a product
media relative to a reference element sealed within the probe body. Since temperature
changes effect the resistance of both the exposed and protected element equally, measuring
the resistance ratio minimizes the influence of changes in the ambient temperature.
Therefore, any net change in the resistance ratio is solely attributable to metal loss from the
exposed element once temperature equilibrium is established.

If the corrosion occurring in the vessel under study is roughly uniform, a change in resistance is
proportional to an increment of corrosion. Although universally applicable, the ER method is
uniquely suited to corrosive environments having either poor or non-continuous electrolytes
such as vapors, gases, soils, "wet" hydro-carbons, and non aqueous liquids.

An ER monitoring system consists of an instrument connected to a probe. The instrument may

be permanently installed to provide continuous information, or may be portable to gather
periodic data from a number of locations. The probe is equipped with a sensing element
having a composition similar to that of the process equipment of interest. The sensing element
itself can be manufactured in one of many geometries:

Wire loop elements are the most common elements available. This type of element has
high sensitivity and low susceptibility to system noise, making it a good choice for most
monitoring installations. Wire loops are generally glass-sealed into an end cap which is
then welded to the probe body.
Tube loop elements are recommended where high sensitivity is required to rapidly
detect low corrosion rates. Tube loop elements are manufactured from a small bore,
hollow tube formed into the above loop configuration. Carbon Steel is the alloy most
commonly used.
Strip loop elements are similar to the wire and tube loop configurations. The strip loop
is a flat element formed in a loop geometry. The strip loop may be glass or epoxy
sealed into the end cap depending on the required application. The strip loop is a very
sensitive element. Strip loops are very fragile and should only be considered for very
low flow applications.
Cylindrical elements are made by welding a hollow tube inside of another hollow tube.
The element has an all welded construction which is then welded to the probe body.
Because of this element's all welded construction, exotic alloy elements can be
produced relatively easily. This probe is ideally suited to harsh environments including
high velocity and high temperature systems, or anywhere a glass-sealed element is not
an option.
Spiral loop elements consist of a thin strip of metal formed on an inert base. The
element is particularly rugged and ideal for high-flow regimens. Its comparatively high
resistance produces a high signal-to-noise ratio, which makes the element very
sensitive.
Flush mount elements are designed to be mounted flush with the vessel wall. This
element is very effective at simulating the true corrosion condition along the interior
surfaces of the vessel wall. Being flush, this element is not prone to damage in high
velocity systems and can be used in pipeline systems that are subject to pigging
operations.
Surface strip elements are thin rectangular elements with a comparatively large
surface area to allow more representative results in non-homogeneous corrosive
environments. Strip elements are commonly used in underground probes to monitor the
effectiveness of cathodic protection currents applied to the external surfaces of buried
structures.

See also:

Corrosion Coupons
Inductive Resistance Probes
Linear Polarization Resistance (LPR)