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CAUSES OF COPPER
CORROSION IN
PLUMBING SYSTEMS

Author: R J Oliphant



A Review of Current Knowledge


FR/R0007
February 2003
Revised May 2003


Foundation for Water Research


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(20% discount to FWR Members)


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The contents of this report are the copyright of the Foundation for Water
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FWR Reviews of Current Knowledge (ROCKs) focus on water-environment
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object of a ROCK is to provide concise, independent scientific and technical
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involved and to promote informed opinion about them
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Causes of Copper Corrosion in Plumbing Systems

Table of Contents

Foreword 4

General Introduction 5

History of copper products in water supply applications 7

An introduction to copper corrosion processes 8

Dissolved and particulate copper in drinking-water 10
Potential problems 10
Cuprosolvency 10
Blue-Water problems 11

Pitting corrosion of copper pipes, fittings and cylinders 13
Introduction 13
Type 1 pitting 15
Type II pitting 18
Rosette corrosion of cylinders 19
Microbiologically induced putting 22
Erosion corrosion 24
Flux induced pitting 25

Problems experienced with copper alloys in water supply 26
Copper alloys 26
Dezincification of brasses 27
Corrosion of gunmetals 29
Lead leaching from copper alloys 29
Problems with solders 30

Concluding comments 30

Glossary of technical terms 31

References 32
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Causes of Copper Corrosion in Plumbing Systems

Author: R. J Oliphant



Foreword

It is a well-attested phenomenon of medical students that, having read a textbook
on human diseases, they become convinced they have at least half the conditions
described and that being alive is a very hazardous undertaking. Similarly, a book
on the problems that have been experienced with copper in plumbing systems
may convince the reader that it is a very hazardous material that should be
avoided as far as possible. As with the medical student and his text book, a sense
of proportion is required and the reader should appreciate that the conditions
described in this booklet are rare when compared with the total length of copper
that has successfully been used in plumbing systems world-wide. Furthermore, a
significant number of the problems that do occur arise from the actions of the
end-user and can be avoided by the application of current knowledge. This last
fact is the reason this review has been prepared.

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General Introduction

This review is intended for anyone with an interest in the design or the
installation of water supply systems using copper pipes or hot water cylinders. It
is relevant to plumbers, water industry staff, architects and property owners.

It covers both hot and cold water supplies inside buildings, but not central
heating systems.

The review describes:
Problems that can occur inside the pipework and fittings of water supply
systems made of copper and copper alloys (such as brass);
How to identify the cause of problems when they do arise; and
How problems might be avoided.

In contact with oxygenated drinking-waters copper develops a semi-protective
corrosion product layer. This usually ensures an economic life for the pipework
and limits the concentration of copper in the water to values well below the
maximum of 2 milligrams per litre (mg/l) allowed under the UK Drinking Water
Regulations (Reference 1). These same regulations control the general
composition of UK public water supplies. In such waters copper pipe is normally
resistant to corrosion. However, problems can occur if a non-protective layer is
formed through prolonged stagnation during a systems early life and in the
presence of certain water characteristics.

The localised breakdown of the protective films that form on copper may lead to
pitting corrosion. The earliest known and most common forms of this mode of
attack are carbon film cold water pitting (also known as Type I), hot, soft water
pitting (also known as Type II) and erosion corrosion. All these forms are
reasonably well understood and effective ways of avoiding them have been
identified. The more recently identified Rosette corrosion, which affects copper
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hot water cylinders with an aluminium protector rod, is now understood and can
be completely avoided by using an improved design of cylinder where the
heating coil is positioned closer to the base (Reference 23).

Microbiologically induced pitting is a more intractable problem because of its
intrinsically complex nature and the practical difficulty of treating a system once
it has become infected. Current understanding only allows the identification of
risk factors and remedies that have been useful in some instances.

In some circumstances copper surfaces may suffer general corrosion because the
water is cuprosolvent or because the local conditions and water composition
create a blue water problem. Cuprosolvency is fairly well understood and in
UK waters is usually readily solved by raising the pH of the supply. The
understanding of blue water problems has only progressed to the identification
of risk factors and to a list of remedies that have been found to be effective in
some cases.

The historical problem with copper alloy fittings, the dezincification of brass, is
now well characterised and alloys that are resistant or immune to this form of
attack have been developed. The future problem with these alloys may be the
leaching of lead that may become significant as the permitted concentration of
lead in drinking-water is reduced over the next decade (Reference 17).

The problems of lead contamination from leaded solders should have already
been confined to history because leaded solders have been banned in the UK for
use with drinking-waters for more than 15 years. Current regulations ban the use
of lead based solders for domestic hot and cold water systems and other
installations where the water is required to be wholesome (see later section
entitled Problems with solders).


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History of copper products in water supply applications

Copper pipes have been used for domestic water services for nearly 200 years.
Before that, water supply pipework was most commonly made from lead. The
introduction of copper pipes offered a stronger, lighter and cheaper alternative.
The first pipes, used in 1810 (Reference 2) were made from sheet metal. Since
then, there have been a number of developments in the manufacture and joining
of copper pipes.
Copper pipes are now used in most domestic and commercial plumbing systems.
1850 onwards Thick (known as heavy gauged) pipes made from sheet metal and
joined by screw threads were being used in hospitals and similar
institutions.

1894 The introduction of the process of extrusion of copper allowed thinner
pipes to be made.

1910 Thinner (known as lighter gauge) pipes first used joined by fine
screw thread or push-fit joint (incorporating a rubber ring).

1921 The Liverpool Corporation started to use light gauge pipes for both
internal and external water supply.

1936 The first British Standard for copper pipes was published. Capillary
(soldered) joints and compression fittings for joining pipe introduced
(see below).

1939 British Standard revised to include capillary (soldered) and
compression fittings.

1996 European Standard BS EN 1057: Copper and copper alloys.
Seamless, round copper tubes for water and gas in sanitary and
heating applications.
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Capillary (soldered) fittings are formed from copper tube or copper alloy by
pressing or stamping. Copper pipe is inserted into the fitting and the assembled
joint is heated to allow solder (which is either end-fed into the joint using solder
wire or included in the fitting during manufacture) to run into the narrow space
between the pipe and the fitting.

Compression fittings are stamped or sand-cast from copper alloys. Once the
pipe is inserted into the body of the fitting, a nut is tightened onto the body
thereby compressing a metal sealing ring (called an olive) that grips onto the
outside wall of the pipe.

A copper alloy is the combination of copper with one or more other metals to
form a material that can improve upon the performance of pure copper. The most
commonly encountered copper alloys are brasses and gunmetals.

Brasses are alloys made primarily from copper and zinc. Brasses can be
used for producing sand-cast fittings and for hot stamped or forged fittings.
Gunmetals are alloys of copper, tin and zinc, which may also contain lead.
They can only be used for manufacturing cast items. Products made from
gunmetal exhibit very few problems in drinking-water but tend to be more
expensive than those made of stamped brass due to the number of rejects
during production.


An introduction to copper corrosion processes

Coppers resistance to corrosion relies upon a small amount of corrosion
occurring at the pipe surface to form a protective (semi-passive) layer that stifles
further corrosion. Whether a significant amount of corrosion occurs, and the type
of corrosion product that is formed, will depend upon the conditions to which the
pipe is subjected.
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1. In water with low oxygen content (less than 2 mg/l of oxygen) the metal
itself is stable and it will not corrode readily.

2. In acidic water (pH less than about 6) with high oxygen content (greater
than 2 mg/l of oxygen), the metal may dissolve to form the copper ion
(Cu
2+
, also called cupric ion), which is the most stable form in these
conditions. Such waters are cuprosolvent and this condition is discussed
later.

3. In around neutral to slightly alkaline water (pH 6 to 8) with high oxygen
content the metal may initially produce an insoluble layer of cuprous oxide
(Cu
2
O). This magenta red to brown corrosion product will be the most
stable species in these conditions and will form a semi-protective scale
against further corrosion.

4. Similarly in water with high oxygen content, which is strongly alkaline (pH
greater than 8), the copper may form a layer of cupric oxide (CuO). This jet-
black to brown corrosion product will be the most stable species in these
conditions and will form a semi-protective scale against further corrosion.

Of these four sets of conditions, only the second leads to uninhibited corrosion.
Where the initial semi-protective scales form (3 & 4 above), corrosion continues,
but at a much-reduced rate. A deposit can form on top of the oxide layer which
typically consists of basic copper carbonate or malachite (Cu
2
(OH)
2
CO
3
). This
deposit has a characteristic turquoise green colour. For malachite to be produced,
the water needs to contain carbonate combined with a sufficiently high pH. The
formation of this copper salt will limit the level of copper dissolved in the water.
The composite deposits are also beneficial for the long-term structural
performance of the pipe, but can experience localised breakdown leading to
different types of pitting corrosion, which are described later.

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For the layers to be protective, periods of prolonged static water conditions have
to be avoided. It is for this reason that systems that have been initially filled, to
establish their hydraulic soundness, but then left standing full of water until the
building becomes occupied, often give unsatisfactory long-term performance.
Consequently, it is recommended that newly completed copper pipework be
drained after testing if it is not to be used within a few days (Reference 19). If
this is not feasible, or if existing pipework is temporarily unused, flushing is
recommended at least weekly to avoid loss of the protective layer (Reference
19).

Dissolved and particulate copper in drinking-water

Potential problems

Copper is an essential nutritional element. According to the World Health
Organization (Reference 3), the human body requires a daily copper intake of 2
to 4 milligrams. The normal sources are food rather than drinking-water.
However, although copper is an essential element, at very high concentrations it
is potentially toxic and so is limited under the UK Drinking Water Regulations
(Reference 1) to a maximum permitted concentration of 2 mg/l.

Consequently, the concentration of copper in the conveyed water is as important
as the effect of the water on the mechanical integrity of the pipework. High
concentrations of copper will occur under conditions where the Cu
2+
ion (cupric
ion) is the stable species (i.e. cuprosolvent water) or where an insoluble copper
corrosion product forms but does not adhere to the pipe wall, creating a blue-
water problem. These problems can be avoided and are described below.

Cuprosolvency

A cuprosolvent water is one in which either the Cu
2+
ion (cupric ion) is the stable
species or in which the copper salts that form on the metals surface are highly
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soluble. The latter situation leads to a thinner and consequently less protective
layer; the result is a corrosion rate nearer to that of the bare metal and high
copper levels in the water. Cuprosolvent waters are normally borehole supplies
(often private) containing an excess of free carbon dioxide, which lowers the pH
of the water and increases the solubility of all the copper corrosion species that
might form. These are the same conditions that cause a water to be
plumbosolvent to lead pipework, leading to the presence of lead in drinking-
water. Most plumbosolvent public water supplies have been identified and are
now treated to prevent plumbosolvency. Those supplies containing excessive
free carbon dioxide are treated to remove this (usually by pH elevation), and as a
consequence cuprosolvency is now rarely encountered. However private
supplies may not be so treated.

Another cause of high copper concentrations is prolonged stagnation of
drinking-water in a plumbing system. In such cases the solution is to reduce
stagnation by redesigning the layout of pipework or by replacing with smaller
diameter pipes.

Blue-Water problems

In some situations, water that has been conveyed or stored in a copper system
may exhibit a characteristic opaque blue colour.

It has been suggested (Reference 4) that cupric hydroxide (Cu(OH)
2
) is the
initial corrosion product that is formed in all aerated waters. Normally, the
cupric hydroxide converts in a relatively short period of time into the more
familiar and much less soluble cuprous oxide (the magenta red to brown layer,
Cu
2
O) and the levels of contamination in the water decrease significantly. Blue-
water problems occur in those waters where the conversion of the cupric
hydroxide is for some reason delayed. The relatively high solubility of this
compound accounts for the high levels of copper found in the water and the
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characteristic blue colour. Unfortunately, the current understanding of this
problem does not allow reliable predictions of where it will occur, only the
identification of risk factors. These include the following, which are listed with
possible scientific explanations.

Low bicarbonate. Low levels (less than 20 mg/l as calcium carbonate) of
bicarbonate (HCO
3
-
ion) in the transported water will prevent the production of
the basic copper carbonate layer, leaving the initial oxide layer less protected.
This alone need not lead to blue water problems if the insoluble cuprous oxide
could still be formed.

High pH water. In high pH water (greater than pH 9), the highly soluble cupric
hydroxide is either the most stable compound and is formed in preference or it
converts only slowly to the more usual and less soluble copper oxides. High pH
will therefore tend to initiate blue water problems.

Microbiological growths. The presence of microbiological growths inhibits the
supply of oxygen to the metals surface and hence the production of the
protective cuprous oxide layer. Low chlorine residuals, temperatures of 25 -
55C, and high assimilable organic carbon content in the water (i.e. material that
bacteria can use as a food source) all encourage microbiological growths.

Sulphate-reducing bacteria or sulphides. These anaerobic bacteria reduce
sulphates to hydrogen sulphide (H
2
S), the presence of which has been proven to
be deleterious to copper even at high pH values.

Stagnation of water early in pipe life. Anaerobic conditions can develop as the
dissolved oxygen in the water becomes consumed as part of the corrosion
reaction. This stifles the production of the protective cuprous oxide layer.
Prolonged stagnation in the early life of the system (e.g. after hydraulic testing
and before going into service), dead-ends and long residence times (e.g. factory
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shutdown periods) should be avoided. See Reference 19 where it is
recommended that newly completed copper pipework be drained after testing if
it is not to be used within a few days, or that the pipework be flushed at least
weekly if not drained.

Solving a severe blue-water problem will depend upon which of the above
factors are identified as contributing to the problem. In some situations an
immediate improvement has been obtained by: -
heat shock using hot water in excess of 60C;
super-chlorination (e.g. 5 mg/l of free chlorine);
replacing afflicted sections of pipe (not effective in presence of sulphate-
reducing bacteria).

Improvements in the long-term may be obtained by: -
maintaining a chlorine residual (to reduce microbiological growths);
adding bicarbonates;
adding polyphosphates (reduces blue water appearance but not copper
concentrations);
lowering the pH to 7.5, although this would not be acceptable where there
was a danger of creating plumbosolvency problems;
redesigning the affected system to ensure minimum water residence times.

However, these solutions are often speculative and best identified by a corrosion
specialist. In most cases the associated costs will confine investigational work to
problems encountered in large buildings and institutions.

Pitting corrosion of copper pipes, fittings and cylinders

Introduction

Copper pipes, fittings and cylinders can exhibit localised breakdown of the semi-
protective scale leading to pitting, which may result in leakage by pinhole
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failures in the pipe wall. For a failure to occur by pitting, certain conditions need
to be present which start the breakdown of the semi-protective scale (initiation
conditions) and furthermore, specific conditions are needed to continue the
process (propagation conditions) in most cases.

Several different types of pitting have been identified which are differentiated by
the conditions required for their occurrence (Table 1).
Table 1. The different types of pitting corrosion found in UK waters.

Type of Pitting Initiation conditions Propagation conditions
Type I Presence of a harmful film
(usually carbon) in the
tube and cold water (less
than 40C)

Unfavourable combination of
six inorganic parameters
Type II Hot, soft water with low
pH
Unfavourable bicarbonate/
sulphate ratio

Rosette corrosion Copper hot-water cylinder
with aluminium protector
rod

Unfavourable ratio of
inorganic anions
Microbiologically
induced corrosion

Development of a
biological film in the pipe
Soft water with high level of
assimilable organic carbon

Erosion corrosion High velocity water

Cuprosolvent water
Flux induced
corrosion
Presence of a flux run


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Each of the types of pitting in the Table above is discussed in more detail below.
However, it must be borne in mind that in many situations there may not be
absolute and clearly identified distinctions between the different types of copper
pitting (Reference 5).

Type I pitting

Type I pitting (or cold water pitting) is confined to those parts of the plumbing
system that never exceed 40C (i.e. in cold water pipes and the bottom of
traditional hot water cylinders where the heating elements were positioned high
above the base).

Characteristic features. Corrosion deposits are deep green, semi-isolated
mounds above pits or pinholes in the pipe wall (see Photographs 1 and 2).
Typically the pipe or cylinder fails in a short period of time, usually between
three and four years but sometimes within a few months. Two or more factors
need to be present for Type I pitting damage to occur.

Initiation of pitting is generally related to the condition of the metal before it is
exposed to water. In pipes, initiation usually occurs due to the presence of a
carbon film produced in manufacture from the pyrolysis of the drawing oils
during the inert gas annealing process (References 6 & 7). The presence of a
continuous carbon film, rather than the quantity of carbon present, seems to be
the key factor in creating this condition.
Technical notes: For Type 1 pitting to initiate, the electrochemical potential of
copper has to be above a critical value (greater than +100 mV against a
standard calomel electrode). Occasionally high electrochemical potentials can
be achieved because of high dissolved copper levels in pipes where cuprosolvent
water has been static for a prolonged period. However, this is usually more of a
problem with copper hot water cylinders; see Rosette corrosion later for
further details.
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The propagation of the pit is normally a function of water quality. The water has
to have a critical composition that is determined by a combination of six
inorganic parameters (dissolved oxygen, sulphate, chloride, nitrate, sodium and
pH).

The British Non-ferrous Metals Technology Centre has developed a nomogram
(Reference 8), which uses these six factors to calculate the Pitting Propensity
Rating (PPR) of a water supply. A positive value for the PPR indicates the water
will propagate the attack, a negative value that it is non-pitting.

Type I pitting does not normally occur under the following conditions:

Water pH less than 7 where more rapid, generalised corrosion will occur;

In surface-derived supplies which normally contain a natural organic
material that inhibits corrosion (Reference 9);

Water with high chloride content (i.e. greater than 60 mg/l) where more
rapid, generalised corrosion will occur.

Typical Type I pitting waters are borehole supplies, which are largely free of
organic matter and have pH values in the range 7 to 8.2.


What to do about it. It is normal practice for manufacturers to take measures to
remove, or prevent the development of, deleterious films. Tubes conforming to
the European Standard BS EN 1057 (Reference 22) should not initiate carbon
film cold water pitting because this standard specifies a carbon content or carbon
film test.
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Photograph 1. Typical distribution of Type I pits in copper pipe















Photograph 2. Detail of a Type I pit with a central mound of malachite above
the initiating site surrounded by secondary mounds above daughter pits.
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Type II pitting

The potential for Type II pitting (or hot soft water pitting) in the UK is much less
than Type I and consequently Type II has not been studied in such depth. It
occurs in hot water systems only (i.e. greater than 60C) and is associated with
very soft waters (usually derived from upland catchments) that often contain
manganese. Type II pitting is much slower than Type I, rarely producing a
perforation in less than eight years.

Characteristic features. Deep pits of small cross-section containing very hard
crystalline cuprous oxide (Cu
2
O) capped by small black or greenish-black
mounds of cuprous oxide and basic copper sulphate.

The occurrence of Type II pitting appears to be primarily related to water
quality, but the mechanism is still in question.

Deposition of manganese. Problems have arisen with waters containing as little
as 30 micrograms per litre (g/l) of manganese. Such waters are normally soft,
upland supplies that have been treated to raise their pH to above 7.4.



Technical notes. The problem is believed to occur when the soluble
manganous ion (Mn
2+
) oxidises to the insoluble manganic ion (Mn
4+
) to form
manganese dioxide (MnO
2
). The latter acts as a powerful cathodic depolariser
(it is used as such in dry cell batteries) and thus stimulates the corrosion
reaction.
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Ratio of bicarbonate to sulphate. In Scandinavia, where Type II is the most
common form of copper pitting, manganese dioxide is not considered an
important factor. Work by Mattsson (Reference 10) suggested that the ratio of
bicarbonate to sulphate (HCO
3
-
/SO
4
2-
), was the critical factor. This work is at
variance with the advice of British workers.

Rosette corrosion of cylinders

Rosette corrosion is a recently recognised phenomenon causing premature
failures in copper hot water cylinders containing an aluminium protector rod (see
technical notes below).

Characteristic features. Heavy sediments of an aluminium corrosion product
that vary from white with a bluish tinge to light green in colour. Underneath
these deposits, the copper is a vivid brick red magenta colour (see Photograph 3)
consisting of large platelets of cuprous oxide separated by deep trenches; hence
the original name Rosette pitting. However, it is probably more accurately
described as a general attack due to the development of highly corrosive
conditions beneath the aluminium corrosion deposits. Failure occurs due to the
thinning of the cylinder wall eventually leading to perforation.

What to do about it. Advice on prevention has centred on creating conditions
that discourage the deposition of manganese dioxide. These include:
Not running the system at temperatures above 60C.
Avoiding oxidising conditions such as over chlorination or entrainment of
air in the system.
Keeping the pH below 7.5, although this would not be acceptable
where there was a danger of creating plumbosolvency problems.
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Photograph 3. View of the internal surface of the base of a hot water cylinder
(after the removal of all loose deposits) showing the broad intensely red
corrosion product layer in the peripheral crevice where Rosette corrosion has
become initiated.
Technical notes. A high electrochemical potential, sufficient to initiate Type I
pitting, can be generated by the presence of high levels of dissolved copper in
the water. Such conditions typically arise at the base of new hot water cylinders
due to initial high corrosion rates of the clean metal walls.

Aluminium protector rods have been successfully used for over thirty years to
prevent Type I pitting in copper hot water cylinders. A rod of pure aluminium is
mechanically attached to the base of the cylinder to form a galvanic couple with
the copper. Preferential corrosion of the more electronegative aluminium
produces a flow of electrons onto the copper, which suppresses the latters
electrochemical potential to below its pitting initiation potential even in the
presence of copper ions. After a few months in service a semi-protective film
forms over upper parts of the cylinder wall, thereby reducing the flow of copper
ions into the water, and the protection of the aluminium rod is no longer needed.
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Research (Reference 11) into the causes of rosette corrosion has established that
the aluminium/copper galvanic couple is so energetic that it does not just
suppress the electrochemical potential of the copper but also reduces any nitrate
(NO
3
-
) in the water to ammonia and some of the sulphate (SO
4
2-
) to sulphide
(S
2-
). Both of these chemical species are highly corrosive to copper. There
appears to be no minimum concentration of either nitrate or sulphate for the
occurrence of Rosette corrosion; however, the relative concentrations of all the
negatively charged ions (called anions) are important. It is thought that all the
anions concentrate around the aluminium rod (the anode of the aluminium/
copper couple) and the extent to which the nitrate and sulphate are reduced
depends on the extent to which they are crowded out by other anions such as
chloride (Cl
-
) and bicarbonate (HCO
3
-
).

In some areas of the UK there has been a general increase in the nitrate
concentration of the water supply. This increase and the critical nature of the
nitrate ion may explain why it has taken thirty years for the problem to be
noticed.

Unfortunately, although Rosette corrosion should now be of historical interest
only, contractors are still specifying cylinders with aluminium protector rods and
manufacturers are still making them to meet this demand. Part of the problem is
What to do about it. The problem of Rosette corrosion has been solved by a
re-design of the hot water cylinder so that an aluminium protector rod is no
longer required (Reference 23). The re-design has involved lowering the
position of the heating coil so that the base of the cylinder operates above 40
o
C. Above this temperature cupric oxide (CuO), rather than cuprous oxide
(Cu
2
O), is the stable species and, not being a semi-conductor, it does not
support Type I pitting.
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the perception that cylinders with aluminium rods are generally protected against
corrosion, rather than just the specific problem of Type I pitting. As a
consequence such cylinders have been used in a wider range of waters than
necessary, i.e. even in waters where Type I pitting did not occur. Whereas in the
past, apart from the unnecessary extra cost, this was of little consequence, now a
contractor runs the risk of experiencing Rosette corrosion with a water that does
not support Type I pitting and so did not require an aluminium protector rod in
the first place.

Microbiologically induced pitting

The presence of biofilms in pipes has led to severe copper pitting in large
institutional buildings, particularly hospitals (Reference 12). The biofilms are
thin, continuous layers of bacteria containing polysaccharides or thick, copious
slimes. They create alternating aerobic/anaerobic environments and promote the
growth of sulphate-reducing bacteria.

Characteristic features. Pitting consists of copper tubercles, often above
multiple initiation sites (pepper pot corrosion), overlaid with a black precipitate
(see Photograph 4). General corrosion also leads to the sporadic release of
copper into the water. Leakage in the pipework occurs as a result of the thinning
of the wall. Pitting can occur in both hot and cold water systems.

A range of factors can promote microbiologically induced pitting. These are
discussed below.

Soft, low-alkalinity water. Low levels of bicarbonate (less than 20 mg/l as
calcium carbonate) in the transported water will prevent the production of the
basic copper carbonate layer, leaving the oxide layer unprotected. Treatment to
reduce this problem includes the addition of carbonate hardness, e.g. by adding
carbon dioxide to the water and passing it through a filter of marble chips.
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High levels of assimilable organic carbon. Organic carbon acts as a food source
for bacteria. Other factors that encourage the growth of bacteria will also
increase the likelihood of microbiologically induced pitting (see blue water
problems).

Stagnation of water early in pipe life (see blue water problems).













Photograph 4. An acid cleaned copper pipe surface showing pepper pot
corrosion produced by microbiological action.
What to do about it. The following actions may be taken: these have been
found to be only partially effective. The choice will depend upon the factors
contributing to the problem.
Clean out the corrosion deposits with a citric acid solution containing
surfactants.
Flush with hot water (greater than 60C) where a cold water system is
affected.
Add carbonate hardness using carbon dioxide and a filter of marble chips.
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Erosion corrosion

Cuprosolvent waters (see section on cuprosolvency) combined with high water
velocities can lead to damage by erosion corrosion. High water velocity in the
pipe leads to mechanical damage of the already thin corrosion product layer and
exposes the bright metal underneath. The bare metal corrodes at a higher rate
than the protected pipe wall.

Characteristic features. Broad horseshoe shaped pits clean of any deposits. The
orientation of the pits indicates the direction of the flow of water horses walk
upstream.

As discussed in the section on cuprosolvency, the water will dissolve the copper
salts that form on the surface of the pipes leading to a thinner and hence less
protective layer.

Technical notes. At restrictions in the copper pipework, or changes in the
direction of flow of the water (e.g. fittings and bends), the water speed increases
and the local pressure drops (the Venturi effect). The drop in pressure causes the
dissolved carbon dioxide to form gas bubbles. Downstream of the restriction or
bend, the water speed and pressure resume their original values. The gas
bubbles collapse as the carbon dioxide dissolves, creating a local water hammer
effect and actual mechanical damage (impingement) of the corrosion layer.

The flow pattern of water through a pipe system is fairly consistent. Therefore
the damage will always occur at approximately the same point and will be very
localised. The exposed bare metal will corrode at a high rate and the water flow
will prevent the formation of any protective layer. The ongoing corrosion of the
bare metal will lead, in time, to perforation of the pipe wall.
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Flux induced pitting

Pitting of copper can be associated with the presence of flux runs in the bore of
the tube. The purpose of flux is to create and maintain oxide free surfaces on the
two pieces of copper during jointing. Such surfaces are necessary if a sound
bond is to be achieved with the solder that is to make the joint. In order to create
the oxide free surfaces, many types of fluxes contain chemicals that are
aggressive to copper (Reference 13). If residues of flux are left in the tube after
the joint has been made, these may continue to corrode the copper. Residual flux
may also affect the quality of the conveyed water including unwholesome levels
of copper through leaching. Therefore, fluxes must meet the requirements of the
Water Regulations Advisory Scheme (WRAS) concerning contamination of
drinking-water (Reference 18).

When heat is applied to melt the solder, any excess flux may flow down the tube
producing a run. If this is not washed out, pitting may subsequently occur.

Characteristic features. Typically multiple pinhole failures around the edge of
the flux run.

What to do about it. A system should be designed for flows between 0.5 and
1.0 m/sec for hot water and 0.5 and 2 m/sec for cold water to avoid erosion
corrosion at the higher velocities and to prevent debris settlement at the lower
velocities. These maximum velocities are lower than the maximum design
flow rates recommended to reduce noise from pipework (Reference 13). Instal-
lation defects (burrs, solder beads etc.) can also change the flow patterns and
should be avoided.
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Problems experienced with copper alloys in water supply

Copper alloys

There are two families of copper alloys commonly used in copper pipework
systems: brass and gunmetal.

Brass is the generic name for alloys made primarily from copper and zinc. The
proportion of zinc is in the range 10 45%. For fittings in water systems, a
single-phase -brass (up to 30% zinc) is generally used for sand-cast fittings and
two-phase (duplex) - brass (~40% zinc) for hot stamped or forged fittings.
Hot stamping produces a smooth surface finish to the final product and, as the
problem of rejects due to casting porosity does not arise, they are cheaper.

Gunmetals are alloys of copper, tin and zinc and may also contain lead. They
can only be used for manufacturing cast items. As with the cast brasses, the
problem of rejects, due to through-wall porosity, adds to the unit cost of these
fittings. One of the functions of the lead in these alloys is to reduce casting
porosity; the lead is the last component to solidify and becomes drawn into any
pores in the solid copper alloy matrix.

Both alloys can be affected by erosion corrosion (see section above) although
brasses are more vulnerable than gunmetals.
What to do about it. Problems may be avoided by : -
using the minimum amount of flux;
using water soluble fluxes and washing the tubes internally after jointing;
following practical advice provided by WRAS (Reference 19) and the UK
Copper Board (Reference 20).
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Dezincification of brasses

Under certain conditions brasses may suffer dezincification, i.e. the selective
dissolution of zinc leaving a porous and low strength copper structure behind.
Dezincification can occur in both hot and cold water systems, but is markedly
quicker in hot water systems.

Characteristic features: the normally yellow brass takes on a black/maroon
colour and/or mechanical failures of spindles occur, or deposition of a
voluminous meringue-like corrosion product.

For a water to support dezincification, certain conditions have to be present
(Reference 14):
To initiate corrosion, the pH has to be 7.6 or above.
To propagate the corrosion the chloride concentration in the water has to be
a third or more of the carbonate hardness (the latter expressed as mg
CaCO
3
/l).

If the pH of the water is in the range 7.6 to 8.2, no build-up of deposit occurs and
it takes about fifteen years for the walls of the fittings to become penetrated.
Consumers do not complain about this form of the problem if only for the fact
that few of them occupy the same house for fifteen years. The snapping of tap
and valve spindles, weakened because of the soft nature of the copper left behind
after removal of the zinc, is another manifestation of the problem.

When the pH of the water is greater than 8.2, the corroded zinc precipitates in
the bore of the fitting, usually as hydrozincite (a basic zinc carbonate) greatly
reducing the flow of water. This form of attack is known as meringue
dezincification and is the form that leads to most frequent complaints from the
consumer because it happens in a relatively short period, typically from six
months to five years (see Photograph 5).
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Technical notes. Dezincification can be prevented entirely in a single-phase
-brass by the addition of a very small amount of arsenic (0.02 0.06%). Alloys
treated in this way are described as dezincification immune. The arsenic is only
effective for -phase structures so that a two-phase, duplex (-) alloy cannot
be made immune. When duplex brasses dezincify, it is primarily the zinc-rich
phase that is at risk of attack.

There is another category of alloys described as dezincification resistant, e.g.
CW602N (formerly designated CZ 132). In these alloys the concentration of zinc
(~ 36%) means the alloy is duplex at elevated temperatures, so that it can be hot
stamped, and single phase at room temperature, so it can be protected from
dezincification by the addition of arsenic.

In order for the arsenic present in the CW602N to be effective against dezincifi-
cation, the brass has to be held after forming at a temperature below that used
for the hot stamping, but above ambient, to give time for the structure to convert
from the duplex - to a single phase. In service, a superficial layer of dezin-
cification may occur until the phase material at the surface has become
exhausted. After this, the corrosion cannot penetrate the continuous wall of
phase material immunised by the arsenic.
Photograph 5. A Brass fitting partially blocked by meringue dezincification
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Corrosion of gunmetals

Gunmetals have good corrosion resistance in drinking-waters. The intrinsically
high corrosion resistance of copper is enhanced by the tin, which produces a
tough surface layer that increases the alloys resistance to erosion corrosion.
Gunmetals do not suffer dezincification because the zinc levels are never high
enough; 15% or more zinc is necessary for dezincification to occur.

Lead leaching from copper alloys

A recent area of research has been the leaching of the lead from copper alloys in
contact with drinking-water. This has arisen because of the planned reduction in
the level of lead allowed in drinking-water. In the new EC Directive (published
in 1998), the current allowable level of lead is 50 g/l (the UK standard since
1989). At the end of 2003 this value will halve and finally move to 10 g/l at the
end of 2013. This last value is being interpreted as a weekly average figure and
the method of taking the water sample to show compliance (not yet agreed) will
have to be chosen accordingly.

The development of a British Standard to demonstrate the acceptability of metals
for use with drinking-water (originally BS 7766:1994 now replaced by DD
256:2002) used copper alloys as the trial material. The test showed that, whereas
all the current alloys commonly used comply with the current 50 g/l standard, it
was not clear if they would all comply with a standard of a weekly average of 10
g/l. The work also established there was no simple relationship between the
lead content of an alloy and the level of contamination it produced (Reference
15).
What to do about it. Use only Dezincification immune or Dezincification
resistant brasses in waters that both initiate and propagate this form of
corrosion.
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Problems with solders

Lead contamination from leaded solders is a problem that should now only be of
interest to the historian, such materials having been banned in the UK for use
with drinking-waters for more than 15 years. Current regulations ban the use of
lead based solders for domestic hot and cold water systems and other
installations where the water is required to be wholesome (i.e. water to be used
for drinking, cooking or food production purposes). A leaflet explaining this
(entitled Using lead-free solder for drinking-water fittings) is available from
the Drinking Water Inspectorate (Reference 21). Related practical advice is
available from the Water Regulations Advisory Scheme (Reference 19) and from
the UK Copper Board (Reference 20).

Some problems have been experienced with the replacement non-leaded solder,
a tin silver alloy with a typical composition of 97% tin, 3% silver and a
maximum of 0.1% lead (Reference 16). This has arisen because of the low
mechanical stability of the solder runs that are flushed out and appear as bits in
the water. Although this is a problem that necessarily diminishes with time,
especial care is needed with these alloys to use the minimum amount of solder
and limit the scale of the initial problem.


Concluding comments

Copper pipework, copper cylinders and copper alloy fittings have evolved to
become the most widely used materials for plumbing systems. This is due to
their properties of ease of use, corrosion resistance, mechanical strength and
resistance to external penetration by liquids and gases, and ability to convey
water without tainting it. However, internal corrosion by the conveyed water can
occur in certain circumstances. This review has identified those circumstances
and where possible, how to avoid or remedy them.
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Glossary of chemical terms

Common Name Chemical formula
Cuprous ion
Cu(I) ion, Cu
+
(colourless solution
disproportionating to Cu
2+
even at low
concentrations in water)
Cupric ion
Cu(II) ion, Cu
2+
(blue aqueous
solution)
Cuprite/cuprous oxide/Cu(I) oxide
Cu
2
O (magenta red to brown colour)
Tenorite/cupric oxide/Cu(II) oxide
CuO (from jet black to brown colour)
Cupric hydroxide
Cu(OH)
2
(sky blue colour)
Malachite/Basic copper carbonate
Cu
2
(OH)
2
CO
3
(turquoise to green
colour)
Brochantite/Basic copper sulphate
CU
4
(OH)
6
SO
4
(deep blue colour)
Hydrozincite/Basic zinc carbonate
Zn
5
(OH)
6
(CO
3
)
2
(white colour)
Anion
Negatively charged atom or molecule
created by addition of an electron e.g.
chloride (CI
-
), sulphate (SO
4
2-
) etc. This
process is the counter balancing reaction to
an ongoing corrosion attack.
Cation
Positively charged atom or molecule
created by loss of an electron e.g. zinc
cation (Zn
2+
) etc. This is the process that
occurs when a metal corrodes
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References
1. England and Wales Statutory
Instrument 2000 No. 3184
The Water Supply (Water Quality)
Regulations 2000, The Stationery
Office, Norwich

2. Skeat, W. O (editor)

Manual of British Water Engineering
Practice. Vol. 1, 4
th
Edition, p. 20. W
Heffer and Sons Ltd. Cambridge, 1969.

3. WHO (World Health Organization)

Guidelines for drinking-water quality.
Volume 2. Second edition. 1996.
Geneva, Switzerland.


4. Edwards, M, Schock, M. R & Meyer,
T. E

Alkalinity, pH and copper corrosion
by-product releases. J ournal of the
American Water Works Association,
March, 1996.


5. Fuji T, Kodama T and Haruo B

The effect of water quality on pitting
corrosion of copper tube in hot soft
water. Corrosion Science, Vol 24, No.
10, pp 901-912. 1984.

6. Campbell, H. S

Pitting corrosion in copper water pipes
caused by films of carbonaceous
material. J ournal of Applied Chemistry,
Vol. 77, 1950.
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33

7. Lucey, V F. Developments leading to the present
understanding of the mechanism of pitting
corrosion of copper. British Corrosion
J ournal, Vol. 7, 1972.

8. Lucey, V. F Pitting corrosion of copper in supply waters:
the effect of water composition. British Non-
ferrous Metals Technology Centre Report
RRA 1838, 1972.

9. Campbell, H. S A natural inhibitor of pitting corrosion of
copper in tap water. J ournal of Applied
Chemistry, 4:633-647, 1954.

10. Mattsson, E and Fredriksson,
A. M

Pitting corrosion in copper tubes Cause of
corrosion and countermeasures. British
Corrosion Journal, Vol. 3, 1968.

11. Oliphant, R. J .

Investigation of Rosette corrosion in copper
hot-water cylinders. The J ournal of the Char-
tered Institution of Water and Environmental
Management, Vol. 14, No. 3, June 2000.

12. Keevil, C. W, Walker, J . T,
McEvoy, J and Colbourne, J . S

Detection of biofilms associated with pitting
corrosion of copper pipe work in Scottish
hospitals. Proceedings of the Biodeterioration
Society Meeting on Biocorrosion, Paris, 1988.
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34
13. BS 6700:1997

Specification for Design, installation,
testing and maintenance of services
supplying water for domestic use within
buildings and curtilages. British
Standards Institution, 389 Chiswick High
Road, London, W4 4BG. www.bsi-
global.com




14. Turner, M.E.D

The influence of water composition on the
dezincification of duplex brass.
Proceedings of the Society of Water
Treatment and Examination. Vol. 10, 162,
1961.

15. Oliphant, R. J

Contamination of potable water by lead
from leaded copper alloys. 2
nd

International Conference on Water
Pipeline Systems 1994. BHR Group
Conference Series Publication N
o.
10.
Mechanical Engineering Publications
Limited (MEP), London. ISBN 0 85298
921 0.


16. BS EN 29453

Specification for Soft Solder Alloys
Chemical compositions and forms. British
Standards Institution, 389 Chiswick High
Road, London, W4 4BG.
www.bsi-global.com


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35
17. Drinking Water Inspectorate

DWI Information Letter 3/2001. Further
Guidance on Requirements to meet New
Lead Standards. www.dwi.gov.uk/regs/
infolett/index.htm (Concerns standards
contained within the EU Council Directive
98/83/EC on the quality of water intended
for human consumption).


18. Water Regulations Advisory Scheme

Water Fittings and Materials Directory.
WRAS, Fern Close, Pen-y-Fan Industrial
Estate, Oakdale, Gwent, NP11 3EH or
www.wras.co.uk


19. Water Regulations Advisory
Scheme

Publication No. 9-04-02. May 2002.
Solders and Fluxes. www.wras.co.uk


20. UK Copper Board

Installation Tips - Fluxes and Solders.
Leaflet available from UK Copper Board,
30/34 New Bridge Street, London, EC4V
6BJ or website at www.ukcopperboard.
co.uk

21. Drinking Water Inspectorate

Information Leaflet Using lead-free solder
for drinking water fittings. www.dwi.gov.
uk/pubs/solder/index.htm


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22. BS EN 1057:1996

Copper and copper alloysSeamless
round copper tubes for water and gas in
sanitary and heating applications. British
Standards Institution, 389 Chiswick High
Road, London, W4 4BG. www.bsi-
global.com


23. BS 1566-1:2002

Copper indirect cylinders for domestic
purposes. Open vented copper cylinders.
Requirements and test methods. British
Standards Institution, 389 Chiswick High
Road, London, W4 4BG. www.bsi-
global.com