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Corrosion of Copper Alloys in Potable

Water Systems
NACE Central Area Conference
October 1-4, 2006
By:
David E. Hendrix, P.E.
The Hendrix Group Inc.
Houston, TX.

Corrosion of Copper Alloys in Potable


Water Systems
Who has copper plumbing in their home?

Corrosion of Copper Alloys in Potable


Water Systems
What we will learn:

Short history of copper use and production


A Little about copper and copper alloy systems
Why coppers for potable water/plumbing systems
Pitting corrosion of coppers in potable waters
SCC of coppers in potable waters
Dezincification of coppers in potable waters
Case histories illustrating failures of coppers in potable waters

Corrosion of Copper Alloys in Potable


Water Systems

Copper probably first came into use as the earliest nonprecious metal employed by the Sumerians and Chaldeans
of Mesopotamia, after they had established their thriving
cities of Sumer and Accad, Ur, al'Ubaid and others,
somewhere between 5,000 and 6,000 years ago.

Corrosion of Copper Alloys in Potable


Water Systems

Homer, following the Greek practice of around 1000 B.C.,


called the metal Chalkos; hence the Copper Age is also
known as the Chalcolithic. Finally, after another thousand
years had elapsed, the words "aes Cyprium" appear in
Roman writings of the Early Christian Era because so much
of the metal came from Cyprus. 'Copper' is the anglicized
version of this Latin phrase.

Corrosion of Copper Alloys in Potable


Water Systems
The earliest definite date usually assigned to true bronze
casting is about 2500 B.C., i.e. 700 years or more after
copper is known to have been in use.
The early coppersmiths learned that when hammered,
copper hardened and, conversely, by heating it softened
again.
When some unknown inventor conceived the idea of
deliberately adding fixed proportions of tin ore to the melt,
he produced true bronze and thereby started the Bronze
Age.
6

Corrosion of Copper Alloys in Potable


Water Systems

The Romans were the first to use brass on any significant scale,
although the Greeks were well acquainted with it in Aristotle's time (c.
330 B.C.). They knew it as 'oreichalcos', a brilliant-and-white copper,
which was made by mixing tin and copper with a special earth called
'calmia' that came originally from the shores of the Black Sea.
Pure zinc was not known until quite modern times, the ore employed
being calamine which is an impure zinc carbonate rich in silica.
The earliest brass was made by mixing ground calamine ore with
copper and heating the mixture in a crucible. The heat applied was
sufficient to reduce the zinc to the metallic state but not to melt the
copper. The vapor from the zinc, however, permeated the copper and
formed brass which was then melted.

Corrosion of Copper Alloys in Potable


Water Systems

Until recently copper ore had to be hand-picked if the


extraction of the metal was to be economical.
Today the great majority of mines contain the metal in finely
disseminated particles which aggregate anything from 2 %
to 1% of copper.
To obtain metallic copper, up to 99 percent of the material
mined must be removed as waste.

Corrosion of Copper Alloys in Potable


Water Systems

Only the flotation process can make this practicable; and


even so, it requires large companies with huge plants,
continuous working and immense capital. In order to smelt 4
million tons of new copper in 1963, nearly 400 million tons
of ore have to be handled and treated in various ways.

Corrosion of Copper Alloys in Potable


Water Systems

The product of flotation is called 'concentrate'. It is passed


on to the smelter and, after further processing, refining is
done in great batteries of electrolytic tanks.
The final products of smelting and electrolytic refining are
cathodes, cast often in the form of copper wirebars and
cakes.* The casting are subsequently worked in various
ways into wrought forms. Re-melted cathodes may also be
cast into ingot bars suitable for the preparation of alloys.

10

Corrosion of Copper Alloys in Potable


Water Systems

The industrial importance of copper in the 20th Century has


been extended by the ease with which it combines with
other metals. Tin and zinc are and always have been the
principal alloying elements, but there are now many others aluminum, beryllium, chromium, manganese, etc. - which
form alloys with special mechanical and physical properties.

11

Corrosion of Copper Alloys in Potable


Water Systems
Copper was first used by man over 10,000 years ago.
For nearly five millennia copper was the only metal known
to man, and thus had all the metal applications.
Early copper artifacts were hammered out from pure copper
found in conjunction with copper-bearing ores in a few
places around the world.
By 5000 BC, the dawn of metallurgy had arrived, as
evidence exists of the smelting of simple copper oxide ores
such as malachite and azurite.
12

Corrosion of Copper Alloys in Potable


Water Systems

By 3000 B.C., silver and lead were being used and the
alloying of copper had begun, first with arsenic and then
with tin.
Copper came from the island of Cyprus-from whence its
name.

13

Corrosion of Copper Alloys in Potable


Water Systems

The Bronze Age suddenly ended at about 1200 BC, with the
general collapse of the ancient world and the interruption of
international trade routes. The supply of tin dried up and the
Iron Age was ushered in, not because iron was a superior
material, but because it was widely available.

14

Corrosion of Copper Alloys in Potable


Water Systems

Due to its high strength, durability and superior heat-transfer


capabilities, copper has long been the material of choice for
both residential and commercial plumbing and heating
systems.
80% of homes in the United States use copper pipe and
fittings.
More than 9 out of 10 plumbers (94%) use copper tube in
their own homes.

15

Corrosion of Copper Alloys in Potable


Water Systems
"Homeowners typically do not worry about their plumbing,
but maybe they should," says CDA president Andrew G.
Kireta, Sr. "It's basically an 'out-of-sight, out-of-mind' issue.

16

Corrosion of Copper Alloys in Potable


Water Systems

Why is copper popular for plumbing applications?

Malleable
Easily joined (soldering)
Impermeable
Wont burn or melt in a fire (residential fires)
Biostatic
Inhibits growth of harmful bacteria

17

Corrosion of Copper Alloys in Potable


Water Systems

Lead has traditionally been used in cast brass plumbing


fixtures to improve machineability and to ensure pressure
tightness.
Pressure tightness is achieved because lead fills
intradendritic voids in castings.

18

Corrosion of Copper Alloys in Potable


Water Systems

Cast red and yellow brasses contain a fine dispersion of


lead particles.
This dispersed lead improves machineability of brass
castings by acting as a cutting tool lubricant.
Lead provides weak points or notches in otherwise continuous
chips, which facilitate their breakages into smaller segments.
This allows machines to run at high speeds and keeps
machining costs low.

19

Corrosion of Copper Alloys in Potable


Water Systems

The most common plumbing brass, UNS Alloy C84400, a


semi-red brass where 3, 7 and 9 represent the nominal
amounts of tin, lead and zinc in the alloy.
The most popular red brass, UNS Alloy C83600 is known as
85 metal or 85-5-5-5. In this alloy, the tin, lead and zinc
contents are equal and are 5% each.

20

Corrosion of Copper Alloys in Potable


Water Systems
Copper plumbing tube has been the industry standard in the
U.S. for the last half century.
By any measure, copper has been very successful as a
plumbing tube material. However, failures do occur, but
they are few and infrequent.

21

Corrosion of Copper Alloys in Potable


Water Systems

Copper and Copper Alloy Systems

22

Corrosion of Copper Alloys in Potable


Water Systems

Wrought Alloys:

Cast Alloys:

Coppers(C10100 - C15999) ***

Coppers(C80000 - C81399)

High Copper Alloys(C16000 - C19999)

High Copper Alloys(C81400 - C83299)

Brasses(C21000 - C49999) ***

Brasses(C83300 - C89999)

Bronzes(C50000 - C69999)

Bronzes(C90000 - C95999)

Copper Nickels(C70000 - C73499)

Copper Nickels(C96000 - C96999)

Nickel Silvers(C73500 - C79999)

Nickel Silvers(C97000 - C97999)


Leaded Coppers(C98000 - C98999)
Special Alloys(C99000 - C99999)

23

Corrosion of Copper Alloys in Potable


Water Systems

Coppers(C10100 - C15999)
C21000-C28999 Copper-Zinc Alloys(Yellow Brasses)
C30000-C39999 Copper-Zinc-Lead Alloys(Leaded Brasses)
C40000-C49999 Copper-Zinc-Tin Alloys(Tin Brasses)

24

25

26

27

28

Corrosion of Coppers in Potable Waters

29

Corrosion of Copper Alloys in Potable


Water Systems

A great deal, but not everything, is known about


corrosion of copper, but theories that have little
scientific basis are constantly surfacing.

30

Corrosion of Copper Alloys in Potable


Water Systems

Copper
corrosion
failures by
category.

31

Corrosion of Copper Alloys in Potable


Water Systems
Results of a Copper Development Association (CDA)
symposium on copper plumbing tube pitting.
Aluminum coagulant water treatments increases general
corrosion but not pitting.
Aluminum and chlorine can act synergistically in regard to
corrosion (a source of aluminum includes Portland cement
lined pipe, which contains 5% aluminum).
Pitting has not been reproduced in the laboratory. Water, which
has caused pitting in the actual installations, has been taken
back to the laboratory and used in testing, but pitting has not
been observed. This implies that copper pitting in potable water
is not a completely understood phenomenon.

32

Corrosion of Copper Alloys in Potable


Water Systems
Microbial induced corrosion (MIC) does occur in copper
even though copper is macro-fouling resistant and has well
documented biostatic/biocidal properties.
When copper fails, it is usually a result of factors outside the
designer's knowledge and control.
Corrosion on the internal surfaces of tubes is typically
associated with contaminants such as excessive flux from
soldering. Also, improper chlorination may cause pitting,
and chlorination, in combination with residual flux, can
result in rapid perforation, sometimes in a matter of days.
Other factors, such as high operating velocities, and burrs
or lips remaining on unreamed cut ends of soldered tubes
can lead to erosion failures.
33

Corrosion of Copper Alloys in Potable


Water Systems
Aggressive "pitting waters" are characterized as having a
pH range of 7.2 to 7.8, high content of CO2, (over 10 ppm),
high total dissolved solids including sulfates and chlorides,
and the presence of dissolved oxygen gas.
A coherent theory, that allows prediction or prevention of
copper pitting, is currently lacking".
Flux plays a large role in pitting perforations.
A variety of human causes are responsible They include
failures related to flux, erosion downstream of burrs,
incomplete soldering leading to crevices, microbiological
action and debris leading to underdeposit corrosion.
34

Corrosion of Copper Alloys in Potable


Water Systems

One presenter reported on the cause of extensive pitting observed


in a new hotel in the Middle East after only one year.It was
determined that water quality was a major factor in the observed
failures.
It was known that a reverse osmosis plant supplied the water,
which was heated and recirculated in a closed loop.
The ID surface was covered with a light green scale with scattered
islands of heavy blue-green deposits (chlorine, sulfur and to a
lesser extent, silicon.)
It was concluded that the water quality was less than ideal and the
high concentrations of contaminants, which can be aggressive to
copper were present.

So What!
35

Corrosion of Copper Alloys in Potable


Water Systems
Conclusions from the Symposium on Pitting of
Copper Plumbing Tube
by any measure, copper is a very successful plumbing tube
material.
failures do occur, but they are few and infrequent.
pitting has not been reproduced under controlled laboratory
conditions.
a coherent theory that allows prediction or prevention of pitting
is currently lacking.
flux induced attack is a major cause of pitting.
pitting can occur under deposits, and crevice attack can be
observed in incompletely filled joints.

36

Corrosion of Copper Alloys in Potable


Water Systems
erosion failures are a result of poor design and installation, as well as
operating at excessive velocities.
MIC is increasing because of increasing recognition as a distinct form
of corrosion, decreasing residual chlorine levels, extended lay-up
times during hydrostatic testing, and higher levels of suspended
solids related to phosphate scale-control programs.
MIC can be mitigated by cleaning to remove organic deposits, use of
biocides-after cleaning if possible, avoiding stagnant conditions, using
thermal shock, eliminating nutrient sources, and increasing pH.

corrosion can be mitigated if:


systems are designed so that velocities do not exceed 4 to 5 fps (
1.2 to 1.5 mps ) in circulating systems.
copper tubing systems are properly installed, without he use of
excessive or unusually aggressive fluxes.
37

Corrosion of Copper Alloys in Potable


Water Systems

hot water heater/storage tank corrosion is prevented.


the water purveyor distribute quality product which does not
contain unacceptable amounts of suspended solids,
dissolved carbon dioxide, microorganisms, aluminum,
dissolved hydrogen sulfide and / or iron.
systems are operated within design parameters including
safe and energy-efficient hot water temperatures between
120F and 130F (49C and 54C).

38

Corrosion of Copper Alloys in Potable


Water Systems
Types of Copper Corrosion

Type I (Cold water pitting)*


Type II (Hot water pitting*
Rosette corrosion
MIC
Erosion-Corrosion*
Flux-induced corrosion
Stress corrosion cracking*
Dezincification*

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Corrosion of Copper Alloys in Potable


Water Systems

Erosion-Corrosion

40

Corrosion of Copper Alloys in Potable


Water Systems
Erosion-Corrosion
Typically occurs in recirculating systems.
A typical hot water recirculating system consists of a piping
loop in which hot water, from hot water tanks or boilers, is kept
circulating by one or more pumps. This permits hot water to
reach most points in the building within relatively short periods
of demand time.
Several factors contribute to the corrosion:

41

Corrosion of Copper Alloys in Potable


Water Systems

Several factors contribute to the corrosion:

Water velocities exceeding 5-feet per second.


Undersized distribution lines, creating high velocities.
Oversized circulating pumps with no bypass.
Multiple and/or abrupt changes in direction
Failure to remove the burr on the inside of the tube after cutting.
Improper solder or brazed joints.
Improper use of throttling valves for system balancing.

Excessive velocity in a hot water recirculating system is typically


the result of using an oversized pump, or undersized distribution
lines.

42

Copper Corrosion vs. Velocity

43

Corrosion of Copper Alloys in Potable


Water Systems
Recommendations to eliminate erosion-corrosion
Design all hot water recirculating systems to keep velocities
below 5 feet per second for temperatures up to 60oC
Flow maximums should not exceed 3 to 4 feet per second for
water >60C.
Make all solder joints according to ASTM B828, "Making
Capillary Joints by Soldering of Copper and Copper Alloy Tube
and Fittings.
Reduce dissolved gasses.
Eliminate burrs.

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Corrosion of Copper Alloys in Potable


Water Systems

Pitting Corrosion of Copper

45

Corrosion of Copper Alloys in Potable


Water Systems

Classification of Pitting Corrosion


Type I (Cold water pitting)
Type II (Hot water pitting)
Type III (Soft water pitting)

46

Corrosion of Copper Alloys in Potable


Water Systems
Type I Pitting
Pits deep and narrow
Results in perforation failure
Pits contain Cu2O with over layer of malachite, calcite or
other copper salts (chlorides)
Occurs in hard, cold well waters between pH 7-7.8
Waters high in sulfates relative to chlorides and
bicarbonates
Stagnation early in life, deposits, high chlorine residuals,
or carbon films

47

Type I (Cold water) Pitting

48

Corrosion of Copper Alloys in Potable


Water Systems
Type II Pitting (hot water)

Pits narrower than in Type I pitting


Results in pipe failure
Cu2O in pits with overlayer of bronchantite and malachite
Occurs in hot waters with pH< 7.2
High sulfates relative to bicarbonates
High temperatures, high chlorine residuals, alum
coagulation.

49

Type II (Hot water) Pitting

50

Corrosion of Copper Alloys in Potable


Water Systems

Type III (soft water) pitting


Pits wide and shallow
Blue water, by-products block passages
Cu2O in pits with overlayer of bronchantite and
malachite
Occurs in soft water with pH>8
Stagnation in early life

51

Corrosion of Copper Alloys in Potable


Water Systems

In contact with oxygenated drinking waters copper develops a


semi-protective corrosion product layer. This usually ensures an
economic life and limits the concentration of copper in the water to
values well below 2 (mg/l).

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.

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Corrosion of Copper Alloys in Potable


Water Systems

In water with low oxygen (DO) content (less than 2 mg/l) copper is
stable and it will not corrode readily.
In acidic water (<pH = 6) with high DO (> 2 mg/l), the metal may
dissolve to form the copper ion Cu2+ (also called cupric ion), which
is the most stable form in these conditions. Such waters are
cuprosolvent.
In neutral to slightly alkaline water (pH 6 - 8) with high DO, the
metal may initially produce insoluble cuprous oxide (Cu2O). This
magenta, red-to-brown corrosion product is the most stable
species in these conditions and will form a semi-protective scale
against further corrosion.
In water with high DO and strongly alkaline (pH > 8), the copper
may form cupric oxide (CuO). This jet-black to brown corrosion
product is the most stable species in these conditions and will
form a semi-protective scale against further corrosion.
53

Corrosion of Copper Alloys in Potable


Water Systems
Where the initial semi-protective scales form, 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
(Cu2(OH)2CO3). This deposit has a characteristic turquoisegreen color.
For malachite to be produced, the water needs to contain
carbonate combined with high pH.
The composite deposits are beneficial but can experience
localized breakdown leading to different types of pitting
corrosion.
54

Corrosion of Copper Alloys in Potable


Water Systems
For the layers to be protective, periods of prolonged static
water conditions have to be avoided.
Systems that have been initially filled but then left standing
full of water until the building becomes occupied often give
unsatisfactory long-term performance.
It is recommended that newly completed copper pipework
be drained after testing if it is not to be used within a few
days.
If this is not feasible, flushing is recommended at least
weekly to avoid loss of the protective layer.

55

Corrosion of Copper Alloys in Potable


Water Systems
Type I Corrosion
Type I pitting (or cold water pitting) is confined to those parts of the
plumbing system < 40C.
Corrosion deposits are deep green, semi-isolated mounds above
pits or pinholes in the pipe wall. Typically the pipe or cylinder fails in
a short period of time, (3-4 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. Initiation usually occurs due to the
presence of a carbon film produced in manufacture.
The presence of a continuous carbon film, rather than the quantity
of carbon present, seems to be the key factor in creating this
condition.
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Corrosion of Copper Alloys in Potable


Water Systems
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
(DO, sulfate, chloride, nitrate, sodium and pH).

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Corrosion of Copper Alloys in Potable


Water Systems
Type I pitting does not normally occur under the following
conditions:
Water pH less than 7 where more rapid, generalized corrosion
will occur;
In surface-derived supplies which normally contain a natural
organic material that inhibits corrosion
Water with high chloride content (i.e. greater than 60 mg/l)
where more rapid, generalized 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.

58

Corrosion of Copper Alloys in Potable


Water Systems
Type II Pitting
The potential for Type II pitting occurs in hot water systems
only (i.e. greater than 60 C) and is associated with very soft
waters that often contain manganese.
Type II pitting is much slower than Type I, rarely producing a
perforation in less than eight years.
Characteristic features include deep pits of small cross-section
containing very hard crystalline cuprous oxide (Cu2O) capped
by small black, or greenish-black mounds of cuprous oxide and
basic copper sulfate.
The occurrence of Type II pitting appears to be primarily
related to water quality, but the mechanism is still in question.

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Corrosion of Copper Alloys in Potable


Water Systems
What to do about Type II Pitting
Not running the system at temperatures above 60 C.
Avoiding oxidizing conditions such as over chlorination or
entrainment of air in the system.
Keeping the pH below 7.5.

60

Duplex Film Model of Copper Corrosion

61

Model of Copper Pit Morphology

62

Copper Corrosion vs. pH

63

Corrosion of Copper Alloys in Potable


Water Systems

Dezincification of Copper Alloys

64

Dezincification of Copper Alloys

Dezincification, was first recognized in the late 1950s.


In its simplest form, dezincification was evident with brass
nuts on tap washers. While in service, the affected nuts
turned pink and disintegrated when the washer was being
changed.
More serious was the corrosion of fittings and valves, which
exhibited a build up of visible white or blue/green deposits
before they leaked.

65

Dezincification of Copper Alloys

It was discovered that the corrosion occurred due to the


composition of some waters reacting with particular brass
alloys (copper and zinc).
Brasses with high zinc content were the ones that suffered
dezincification when exposed to aggressive water.
Brasses with >15% zinc the most susceptible to
dezincification.

66

Dezincification of Copper Alloys


The affected metals consisted of two phases and it was the
zinc rich phase that was attacked, with zinc being leached
from the metal and the copper being re-deposited in a pink,
spongy, brittle form.
Whitish deposits, attached to failed valves, consisted of
zinc-rich products.

67

Waters Causing Dezincification

68

Dezincification of Copper Alloys

Dezincification resistant brasses


First generation brasses inhibited with Antimony or Arsenic
C44300, C44400, C46500
The above not immune to dezincification!

69

Dezincification of Copper Alloys


As a result of comprehensive research, laboratory tests and
field trials, dezincification resistant (DR) brass was
developed.
Inhibition to dezincification was achieved, without affecting
the intrinsic properties of brass, by adding small amounts of
certain elements to the alloys.
The metals were also processed in such a way as to reduce
the size of the boundaries of the susceptible zinc-rich phase
to minimize the potential for attack.

70

Dezincification of Copper Alloys


Dezincification resistant brass
Brass contains a mixture of alpha and beta phases, and a
fine distribution of lead particles, which impart excellent
machineability.
In binary brasses, zinc is soluble in copper up to 37% and
exhibits an all alpha phase; further increases in zinc results
in the appearance of the second phase, beta.
The two phases, alpha ductile at room temperature, and
beta easily hot worked, is the key to wide range and
unique fabrication properties of extruded brass. However
the beta phase is particularly vulnerable to dezincification.

71

Dezincification of Copper Alloys


For maximum protection against dezincification, while still
retaining the ease of fabrication, three factors have to be
balanced to achieve the ideal structure with a minimum beta
content.
Careful control of time and temperature during manufacture,
which may include a special heat treatment.
A slight increase in copper content to minimize the
proportion of the beta phase
The addition of a small amount of arsenic which implies
protection to the alpha phase.
72

Present Generation Dezincification Brass

73

Corrosion of Copper Alloys in Potable


Water Systems

Stress Corrosion Cracking of Copper Alloys

74

Stress Corrosion Cracking of Copper Alloys


The main cracking agent of copper and copper alloys is
ammonia or its compounds.
Other cracking agents mentioned in the literature include:

Acetates
Amines
Chlorates
Citrates
Mercury
Nitrates
Nitrites
Moist Sulfur Dioxide

75

Stress Corrosion Cracking of Copper Alloys

No known tensile stress threshold


No known threshold ammonia concentration
Not sensitive to material strength
Stress-corrosion cracking occurs in a great variety of
brasses that differ widely in composition, degree of purity,
and microstructure

76

Stress Corrosion Cracking of Copper Alloys

Cracking occurs only in objects that are subjected to


external or internal stresses
Visible corrosion is frequently associated with the effect, but
the corrosion may often be superficial
Sufficient and continuous coatings of a metal, such as
nickel, confer complete protection.

77

Stress Corrosion Cracking of Copper Alloys

Cracks often follow an intercrystalline path


Traces of NH3 in the environment are an important agent in
inducing SCC in atmospheric exposure
Ammonia has a specific and selective action on the material
in the grain boundaries of brass
Highly stressed articles may be kept for years in a clean air
atmosphere without developing cracks
Ammonia and ammonium salts induce cracking
Surface defects which localize stresses, do not appear to
contribute to the development of cracks in the absence of
an essential corroding agent, such as NH3.
78

Stress Corrosion Cracking of Copper Alloys

Cracking always begins in surface layers that are under


tension
The behavior of a copper alloy subjected to the combined
effect of tensile stress and NH3 is an index of susceptibility
to SCC
Susceptibility to SCC diminishes as the copper content of
the brass is increased
Protracted heating of 70Cu-30Zn brass at 100 C (212 F)
does not develop cracks and does not reduce the internal
stress appreciably

79

Relative
ranking of
copper alloys
susceptibility to
ammonia SCC.

80

Corrosion of Copper Alloys in Potable


Water Systems

Case History 1
SCC of Copper Alloy C44300
(Arsenical Admiralty)

H26087

81

Case History 1 SCC


Background
In service for ~ four years
Repetitive failures
Cooling water treated with amines
Environmental Conditions
Stab-in bundle In a recirculating water cooling tower
OD exposed to cooling water
ID exposed to ethane/propane at 450 psig and 100F

82

Case History 1 SCC


As-received tube samples

83

Case History 1 Split with dent

84

Case History 1 Close-up of split

85

Case history 1 Microstructure with crack

86

Case History 1 High mag view of crack

87

Case History 2 Dezincification

Case History 2
Dezincification Study of Different Brasses

H24130-H25036-H25136-H26036H26058

88

Case History 2 Dezincification of Brass


Switches monitor (detect) flow in municipal or well water
Potable waters of various quality
High temperatures 180F-190F when flowing

89

Case History 2 Dezincification of Brass


Merinque deposits in switch contained:

90

Case History 2 Dezincification of Brass


Client tried electroless nickel (EN) coating the switches

Internal as-cast body


interior

Machined hole area

91

Case History 2 Dezincification of Brass

EN coated
switch
showing
merinque
dezincification

92

Case History 2 Dezincification of Brass


Client tested four different alloys to ISO 6509
Determination of Dezincification Resistance of Brass
Alloy A C83600 (CuZn5Sn5Pb5)
Alloy B (DZR) CW602N (CuZn36Pb2As)
Alloy C C85800 (CuZn40Sn1Pb1)
Alloy D Red Brass (CuZn15)
Alloy E Generic, hardware store yellow (DZR heat
treated, no As) brass

93

ISO 6509 Determination of Dezincification


Resistance of Brass

Exposure to 1% copper (II) chloride solution followed by


microscopic examination.
Temperature at 75F
Immerse samples for 24 hours
Microscopically observe for dezincification

94

ISO 6509 Test Apparatus

95

ISO 6509 Test Sample

96

Case History 2 Alloy A ISO 6509 Result

C83600 - No dezincification

97

Case History 2 Alloy B ISO 6509 Result

C35300 (DZR) - Minor


dezincification
98

Case History 2 Alloy C ISO 6509 Result

C85800 Major dezincification


99

Case History 2 Alloy D ISO 6509 Result

C83600 (Red brass) - No


dezincification
100

Case History 2 Alloy E ISO 6509 Result

Generic hardware store yellow


DZR brass- Major dezincification

101

Case History 3 Erosion-Corrosion

Case History 3
Erosion-Corrosion of Copper Tubing in a
Recirculating Hot Water Loop

H2056

102

Case History 3 Erosion-Corrosion


Background/Process

Hot water system in a 5-star resort


Hot water was in a pumped, recirculating loop
Water temperature >140F (for brief period)
Failures due to pin-hole perforation
Failures began ~1 year after service, accelerated ~3-4
years after start-up.
System included a Byron indirect water boiler, cement
lined storage tanks, and a T&S exchanger.

103

Case History 3 Erosion-Corrosion


Water source and quality
Aquifer water
Water low in hardness, low in chlorides, low in pH (5.86.2) and significant dissolved gases (DO and CO2).
Negative to slightly positive Langelier Index.
No chlorination or fluorination.

ID corrosion products
Cu2O, CuO, CuCO3.Cu(OH2), (assumed from elemental
species).

104

Case History 3 Erosion-Corrosion

105

Case History 3 Erosion-Corrosion

106

Case History 3 Erosion-Corrosion

107

Case History 4 Type I (Cold Water) Pitting


Corrosion

Case History 4
Type I (Cold Water) Pitting Corrosion of
Enhanced C12220 Copper Tubes in AirConditioning Chiller Service

H2244

108

Case History 4 Type I (Cold Water) Pitting


Corrosion
Background:
Air-conditioning Chiller using B359 C12220 copper tubes
Tubes have integral (enhanced) heat transfer fins on the
OD
ID contained cooling water on the tube side
OD contained HCFC 123 refrigerant on the shell side
Tubes failed due to ID perforation after < 1.5 years
service

109

Case History 4 Type I (Cold Water) Pitting


Corrosion
Process Conditions
Tube side softened (well) water mixed with DI water

110

Case History 4 Type I (Cold Water) Pitting


Corrosion

111

Case History 4 Type I (Cold Water) Pitting


Corrosion
Red ID Deposits

O = 0.83%
Si = 0.14
S = 0.10
Fe = 0.18
Cu = 98.75
Al
Cl
Ca

Green ID Deposits
3.57%
0.64
4.17
1.44
86.27
0.12
1.25
2.02

112

Case History 4 Type I (Cold Water) Pitting


Corrosion

ID pit and pit


deposits

113

Case History 4 Type I (Cold Water) Pitting


Corrosion
Summary Conclusions
Tubes experienced Type I pitting corrosion
Mitigating water chemistry
Well water
High sulfate-to-chloride ratio
High residual chlorine (>3 ppm)
High suspended solids (erosive)

114

Case History 5 Copper Tube Corrosion


due to Exposure to Ammonia

Case History 5
Uniform corrosion of ASTM copper tubing in an a
S&T air dryer near an animal waste plant

H23060

115

Case History 5 Copper Tube Corrosion


due to Exposure to Ammonia
Background
Shell and Tube (S&T) Air Dryer experiencing repetitive
failure of B88 Type K copper tubes
Moisture saturated compressed air on TS (100F-38F)
Refrigerant on the SS
Tube failures were on the ID (air side)
Air intake near a pit containing animal waste products
pH of condensed water >8

116

Case History 5 Copper Tube Corrosion


due to Exposure to Ammonia

As-received exchanger tubes

117

Case History 5 Copper Tube Corrosion


due to Exposure to Ammonia

Exchanger manifold

118

Case History 5 Copper Tube Corrosion


due to Exposure to Ammonia

Close-up of
exchanger
manifold showing
rivulet corrosion

119

Case History 5 Copper Tube Corrosion


due to Exposure to Ammonia

Exchanger tube ID
showing general
corrosion

120

Case History 5 Copper Tube Corrosion


due to Exposure to Ammonia

121

Corrosion of Copper Alloys in Potable


Water Systems

The End

122