3.

07 Corrosion of Copper and its Alloys

C. D. S. Tuck
Lloyd’s Register EMEA, London, UK
C. A. Powell
Copper Development Association, Hemel Hemstead, UK
J. Nuttall
European Copper Institute, Belgium

ß 2010 Elsevier B.V. All rights reserved.

3.07.1 Introduction 1938

3.07.1.1 Alloy Compositions and Properties 1938
3.07.1.1.1 Coppers 1938
3.07.1.1.2 High conductivity coppers 1942
3.07.1.1.3 Heat treatable copper alloys 1942
3.07.1.1.4 Brasses 1942
3.07.1.1.5 Cupronickel alloys 1942
3.07.1.1.6 Tin bronze 1943
3.07.1.1.7 Aluminum–bronzes 1943
3.07.1.1.8 Silicon–bronzes 1943
3.07.1.1.9 Nickel silvers 1943
3.07.1.1.10 Copper–nickel–chromium 1943
3.07.2 Theoretical Aspects of Copper Corrosion 1943
3.07.2.1 Electrode Potential Relationships 1944
3.07.2.2 Behavior of Copper Electrodes 1944
3.07.3 Corrosive Environments Experienced 1946
3.07.3.1 Atmospheric Corrosion 1946
3.07.3.2 Soil Corrosion 1949
3.07.3.3 Corrosion in Natural Waters 1950
3.07.3.3.1 Impingement attack 1950
3.07.3.3.2 Dezincification of brasses 1952
3.07.3.3.3 Selective attack in other alloys 1954
3.07.3.3.4 Deposit attack and pitting 1954
3.07.3.4 Corrosion in Freshwater 1954
3.07.3.4.1 Pitting 1954
3.07.3.4.2 Chemical attack 1956
3.07.3.4.3 Microbiologically influenced corrosion 1956
3.07.3.4.4 Stress corrosion cracking 1957
3.07.3.4.5 Dissolution 1957
3.07.3.5 Corrosion in Seawater 1958
3.07.3.6 Effect of Exposure to Contaminated Environments 1960
3.07.3.6.1 Stress corrosion of brasses 1961
3.07.3.6.2 Stress corrosion of other copper alloys 1962
3.07.3.7 Corrosion in Industrial Chemicals 1962
3.07.3.7.1 Acid solutions 1963
3.07.3.7.2 Neutral and alkaline solutions 1963
3.07.3.7.3 Hydrogen sulfide pollution 1963
3.07.3.7.4 Other chemicals 1964
3.07.3.8 High Temperature Oxidation and Scaling 1965
3.07.3.8.1 High temperature oxidation of copper 1965
3.07.3.8.2 High temperature oxidation of copper alloys 1966
3.07.4 Protective Measures 1966

1937
1938 Non-Ferrous Metals and Alloys

3.07.5 Areas of Future Development 1967

3.07.5.1 Antimicrobial Benefits of Copper Corrosion 1967
3.07.5.2 Alloy Developments 1967
References 1968

prehistoric times, and their present-day importance

Glossary
is greater than ever before. Their widespread use
Antimicrobial Capable of destroying or inhibiting
depends on a combination of good corrosion resis-
the growth of microorganisms.
tance in a variety of environments, excellent work-
Dealloying A corrosion process whereby one
ability, high thermal and electrical conductivity, and
constituent of a metal alloy is preferentially
attractive mechanical properties at low, normal, and
removed from the alloy, leaving an altered
moderately elevated temperatures.
residual microstructure.
A wide range of cast and wrought alloys is avail-
Dezincification A corrosion process specific to
able. For detailed expositions of properties and
brasses (copper–zinc alloys) whereby
uses, the reader is referred to publications of many
zinc is preferentially removed from the
specialized aspects obtainable from the Copper
alloy, resulting in a porous residual
Development Association offices in various countries.
microstructure.
Relevant publications of the British Standards
Shape memory alloy An alloy which, after it is
Institution include BSEN1982, Copper Alloy Ingots
deformed, will automatically regain its
and Castings,1 and those covering wrought products.2,3
original geometry when it is heated.
All ASTM standards relating to copper and copper
alloys are included in a volume published annually.4

Abbreviations 3.07.1.1 Alloy Compositions and Properties

BTAH Benzotriazole
The mechanical properties of wrought alloys5,6
FPSO Floating production, storage and offloading
depend on composition and metallurgical condition.
vessel
At the extremes, annealed pure copper has a tensile
MIC Microbiologically influenced corrosion
strength of 220 MN m
2 and a hardness of 40 HV,
MRSA Meticillin-resistant Staphylococcus aureus
and heat-treated beryllium copper can have a tensile
SCC Stress corrosion cracking
strength of 1450 MN m
2 and a hardness of 400 HV.
SEM Scanning electron microscopy
Summaries of typical properties of some of the more
STEM Scanning transmission electron microscopy
important wrought and cast copper alloys are given
WHO World Health Organization
in Tables 1–4.

3.07.1.1.1 Coppers
Symbols The purest grade of copper commercially available,
Ai Activity of species i and that with the highest electrical conductivity, is
K Equilibrium constant and rate constant oxygen-free high-conductivity copper. The minimum
Q Activation energy copper content required by some specifications is
R Copper run-off rate 99.99% and the method of manufacture is such that
R Gas constant no residual deoxidant is present. Oxygen itself has very
T Temperature (K) little effect on conductivity, and the ‘tough pitch’ cop-
pers (either electrolytic or fire-refined), containing
0.04% oxygen are high-conductivity materials.
One disadvantage of tough pitch coppers is embrit-
3.07.1 Introduction tlement, which is liable to occur when they are heated
in atmospheres containing hydrogen. Therefore, for
Copper and copper alloys are among the earliest many purposes (and particularly where fabrication is
metals known to man, as they have been used from involved) deoxidized coppers are preferred. The usual
Table 1 Compositions of wrought copper alloys.2

Alloy

Description EN No. Cu Al Fe Mn Ni P Pb Si Sn Zn Other

HC copper CW004A 99.90Min 0.005 0.0005Bi 0.040 O

Cu–ETP
Deoxidized CW024A 99.90Min 0.015–0.040
nonarsenical
copper
Cu–DHP
Oxygen-free CW008A 99.95Min 0.005 0.0005Bi
copper, Cu–OF
Silver-alloyed CW012A Rem 0.06–0.08Ag
copper, 0.0005Bi 0.040
Cu–EPT O
Tellurium copper CW118C Rem 0.003–0.012 0.4–0.7Te
Beryllium copper CW100C Rem 0.2 0.3 1.6–1.8Be 0.3Co
85/15 brass CW502L 84.0–86.0 0.02 0.05 0.3 0.05 0.1 Rem
70–30 brass CW505L 69.0–71.0 0.02 0.05 0.3 0.05 0.1 Rem
60/40 brass CW509L 59.5–61.5 0.05 0.02 0.3 0.3 0.2 Rem
Dezincification CW602N 61.0–63.0 0.05 0.1 0.1 0.3 1.7–2.8 0.1 Rem 0.02–0.15 As
resistant brass
Free machining CW614N 57.0–59.0 0.05 0.3 0.3 2.5–3.5 0.3 Rem
brass

Corrosion of Copper and its Alloys

Aluminum brass CW702R 76.0–79.0 1.8–2.3 0.07 0.1 0.1 0.01 0.05 Rem 0.02–0.06As
Naval brass CW712R 61.0–63.0 0.1 0.2 0.2–0.6 1.0–1.5 Rem
High tensile CW705R 65.0–68.0 4.0–5.0 0.5–3.0 0.5–3.0 1.0 0.2–0.8 0.2 Rem
brass
18% Nickel CW409J 60.0–63.0 0.3 0.5 17.0–19.0 0.03 0.03 Rem
silver
5% Tin bronze CW451K Rem 0.1 0.2 0.01–0.4 0.02 4.5–5.5 0.2
Silicon bronze CW116C Rem 0.05 0.2 0.7–1.3 0.05 0.05 2.7–3.2 0.4
High strength CW111C Rem 0.2 0.1 1.6–2.5 0.02 0.4–0.8 Additions of Co,
bronze Mg, Cr
10% Aluminum CW307G Rem 8.5–11.0 3.0–5.0 1.0 4.0–6.0 0.05 0.2 0.1 0.4
bronze
90–10 CW352H Rem 1.0–2.0 0.5–1.0 9–11 0.02 0.02 0.03 0.5
Cupronickel
70–30 CW354H Rem 0.4–1.0 0.5–1.5 30–32 0.02 0.02 0.05 0.5
Cupronickel

1939
Values are given in % mass fraction and are maximum values unless indicated otherwise.
 1940
Non-Ferrous Metals and Alloys
Table 2 Typical properties of wrought alloys

Alloy Melting Density Coeff of expansion Electrical Thermal Tensile Elongation Hardness
point ( C) (g cm
3) ( 10
6  C
1) Cond (% conductivity (W Strength (MN (%) (HV)
Description EN No. IACS) mK
1) m
2)

HC copper Cu–ETP CW004A 1083 8.94 18 103 390 220–385 4–55 40–110
Deoxidized CW024A 1082 8.93 18 80 340 220–385 4–60 40–120
nonarsenical copper
Cu–DHP
Oxygen-free copper, CW008A 1083 8.94 18 100 395 220–385 4–60 40–110
Cu–OF
Silver-alloyed copper, CW012A 1083 8.94 18 102 390 220–385 4–55 40–110
Cu–EPT
Tellurium copper CW118C 1075 8.93 18 96 360 250–360 2–7 90–110
Beryllium copper CW100C 955 8.2 18 23 85 680–1450 3–35 100–400
85/15 Brass CW502L 1025 8.74 19 35 155 260–420 4–50 55–135
70–30 Brass CW505L 955 8.53 20 27 125 270–490 9–50 55–150
60/40 Brass CW509L 905 8.38 21 29 125 340–480 6–43 85–140
Dezincification resistant CW602N 8.43 21 26 117 280–520 15–45 70–140
brass
Free machining brass CW614N 8.47 21 27 120 350–450 20–30 100–150
Aluminum brass CW702R 980 8.33 19 23 100 300–390 25–35 70–110
Naval brass CW712R 890 8.41 21 25 110 340–460 10–30 85–140
High tensile brass CW705R 890 8.35 21 23 105 550–650 8–12 150–200
18% Nickel silver CW409J 8.69 16 7 35 380–900 2–40 85–230
5% Tin bronze CW451K 1050 8.89 18 17 80 340–740 1–60 70–220
Silicon bronze CW116C 1030 8.52 18 8 40 380–900 3–50 90–220
High strength bronze CW111C 1060 8.86 17 50 220 600–800 5–15 100–250
10% Aluminum bronze CW 307G 1075 7.5 18 8 40 430–770 15–25 200–240
90–10 cupronickel CW352H 1150 8.91 16 10 50 290–520 8–35 80–160
70–30 cupronickel CW354H 1240 8.94 16 5 30 350–520 12–35 90–130
Table 3 Compositions of cast copper alloys1

Alloy

Description EN No. Cu Al Fe Mn Ni P Pb S Sb Si Sn Zn Other

High CC040 Not

conductivity specified
copper
Dezinification CC752S 61.5–64.5 0.3–0.70 0.35 0.15 0.25 1.5–2.5 0.15 0.02 0.4 Rem 0.15As
resistant
brass
High tensile CC765S 57.0–65.0 0.5–2.5 0.5–2.0 0.5–3.0 6.0 0.03 0.5 0.08 0.1 0.1 Rem
brass
Tin bronze CC481K 87.0–89.5 0.1 0.1 0.05 0.1 0.5–1.0 0.25 0.05 0.05 0.01 10.0–11.5 0.05
Leaded CC491K 83.0–87.0 0.1 0.3 2.0 0.10 4.0–6.0 0.1 0.25 0.01 4.0–6.0 4.0–6.0

Corrosion of Copper and its Alloys

gunmetal
Aluminum CC331G 83.0–89.5 8.5–10.5 1.5–3.5 1.0 1.5 0.1 0.2 0.2 0.5 0.05Mg
bronze
Copper nickel CC382H Rem 0.01 0.5–1.0 0.5–1.0 29.0–31.0 0.01 0.005 0.01 0.15–0.50 0.2 1.5–2.0Cr,
chrome 0.15Zr
0.25Ti
Copper CC140C Rem 0.4–1.2Cr
chromium

Values are given in % mass fraction and are maximum values unless indicated otherwise.

1941
1942 Non-Ferrous Metals and Alloys

Table 4 Properties of cast copper alloys1

Alloy Tensile strength, Elongation, Brinell hardness HB,

minimum (MN m
2) minimum (%) minimum
Description EN No.

High conductivity copper CC040A 150 25 40

Dezincification resistant brass CC752S 280 10 70
High tensile brass CC765S 500 18 120
Tin bronze CC481K 350 4 85
Leaded gunmetal CC491K 230 10 65
Aluminum bronze CC331G 550 18 130
Copper nickel chrome CC382H 440 18 115
Copper–chromium CC140C 300 10 95

deoxidizing agent is phosphorus, and specifications reach tensile strengths of around 800 MN m
2 while
require residual phosphorus contents of between retaining its high conductivity. For this material,
0.004% and 0.06%. Phosphorus-deoxidized coppers which is widely used for plastic moulding equipment,
with lower phosphorus content have electrical con- the main precipitating phase is Ni2Si. Stress relaxa-
ductivities 98% of that of pure copper. tion and the ability to withstand high temperatures
under stress without losing spring properties or ease
3.07.1.1.2 High conductivity coppers of bending are importance for this material.
Pure copper has the highest electrical conductivity of The highest strength of any copper alloy (up to
any metal apart from silver. However, it has poor 1450 MN m
2) is obtained by precipitation hardening
strength and suffers from creep at temperatures above and cold working copper–beryllium (1.8–2.0% Be).
150  C. A small addition of silver (0.03–0.12%) gives However, due to the toxic nature of beryllium, care
an increase in creep strength and resistance to soften- must be exercised in melting and machining this alloy.
ing up to 250  C (up to 350  C for short times).
Copper–silver alloys are widely used in electrical 3.07.1.1.4 Brasses
motors and for contact and catenary wires for electric Brasses are basically alloys of copper and zinc, con-
railways and tramways. They have a nominal conduc- taining between 10% and 45% Zn, but many other
tivity of 100% IACS. In the past, copper–cadmium additions can be made.7 The single-phase (a) brasses,
alloys (0.5–1.2% Cd), which have an excellent combi- containing up to 37% Zn in the binary alloys, may
nation of strength and electrical conductivity, were have additions of 1% Sn (Admiralty brass), 2% Al
widely used for such applications. However, due to (aluminum brass), or 1–3.5% Pb for ease of machin-
health concerns regarding cadmium when the alloy is ing. Duplex (a–b) brasses containing more than 37%
molten, the use of copper–cadmium alloys is declining. Zn, may have additions of 1% Sn (Naval brass), or 1–
Other high conductivity alloys such as copper– 3% Pb to assist machining. Both a and a–b brasses,
magnesium and copper–tin (0.1–0.5%) have been with and without lead, are used in the cast as well as
developed. For all of these high conductivity alloys, a the wrought form. High-tensile brasses are a–b alloys
compromise has to be made between high strength and containing up to 5% Al and 1–2% of one or more of
electrical conductivity. the following: Sn, Pb, Fe, or Mn. These alloys also are
used in both wrought and cast form.
3.07.1.1.3 Heat treatable copper alloys
Copper alloyed with 0.5–1.2% chromium with or 3.07.1.1.5 Cupronickel alloys
without 0.03–0.3% zirconium gives precipitation Cupronickel alloys contain between 5% and 30% Ni
hardening alloys with strengths up to 450 MN m
2. and are mainly used in the wrought condition.8 The
Such alloys have electrical conductivities of 80% more popular grades have 10% and 30% Ni and are
IACS together with good thermal conductivity recognized for their very good corrosion and biofoul-
properties. ing resistance in marine applications.9,10 Small con-
Precipitation hardening Cu–Ni–Si alloys are also trolled alloying additions of iron and manganese are
available. One type is based on copper, nickel, and essential to optimize their resistance to localized cor-
silicon (described as ‘High strength bronze’ in rosion and seawater flow. The addition of chromium
Table 3), which, with further alloy additions, can has also been shown to improve resistance to flow
 Corrosion of Copper and its Alloys 1943

velocity and a cast (30Ni–1.6Cr)11 as well as a wrought 3.07.1.1.9 Nickel silvers

version (16Ni–0.5Cr)12 have been developed. The cast Nickel silvers do not contain silver but are essentially
version has been predominantly used by the British copper–zinc brasses with nickel in the range of
Navy and is covered by DEF STAN 02-824.11 9–18%. The 18% nickel alloy polishes to a white
Other higher strength cupronickels have additions color (like silver) and has good corrosion resistance.
of aluminum or tin, producing two ranges of pro- All have excellent ductility and are available as tube,
ducts. The Cu–Ni–Al alloys13 are thermally age- wire, plate, sheet, and strip.
hardened to form Ni3Al precipitates in the matrix
whereas Cu–Ni–Sn alloys display spinodal strength- 3.07.1.1.10 Copper–nickel--chromium
ening through the development of submicroscopic Copper–nickel–chromium alloys have been devel-
chemical composition fluctuations.14 oped chiefly as cast alloys, the most prominent of
which is CC382H. A version of this is DEF STAN
3.07.1.1.6 Tin bronze 02-824, which is commonly used by the British Navy.
Copper alloys with 1.5–9% Sn and 0.01–0.4% P are
wrought alloys known as phosphor bronzes. They
have good elastic properties combined with good 3.07.2 Theoretical Aspects of Copper
resistance to corrosion and corrosion fatigue. Corrosion
Cast copper alloys with between 2% and 11% Sn
and 1–10% Zn are termed gunmetals. Modified Copper is the first member of Group IB of the peri-
forms may contain lead (up to 7%) giving leaded odic table, having atomic number 29 and electronic
gunmetal or nickel (up to 6%) giving a nickel gun- configuration [Ar]3d104s1. Loss of the outermost
metal. Gunmetals are the most widely used copper s electron gives the cuprous ion Cu+ and a second
casting alloys combining good corrosion resistance electron may be lost from the filled d shell to form the
with modest strength and good castability. cupric ion Cu2+. The availability of the d electrons
for coordination allows copper to readily form com-
plexes with such species as NH3 and CN.
3.07.1.1.7 Aluminum–bronzes Copper occurs in the uncombined state in nature
Wrought aluminum bronzes contain between 4% and and is relatively easily obtained by the reduction of its
12.5% Al. If less than 8% Al is present, the alloys are compounds. It is not very active chemically and oxi-
a-phase and may be cold worked. The two phase dizes very slowly in air at ordinary temperatures. In
(a–b) alloys, which may be wrought or cast, contain the electrochemical series of elements, copper is near
8–12.5% Al with possible additions of iron (0.5–7%), the noble end and will not normally displace hydro-
manganese (1.5–3.5%), nickel (2–7%), and silicon gen, even from acid solutions. Indeed, if hydrogen is
(2%). In terms of its influence on corrosion resis- bubbled through a solution of copper salts, copper is
tance, the addition of nickel is the most important, slowly deposited, a process which occurs more rap-
as it acts to reduce dealuminification (see Section idly if it is carried out under pressure.
3.07.3.3.3). As copper is not an inherently reactive element, it
Aluminum bronzes can be hardened by heat treat- is not surprising that the rate of corrosion, even if
ment and have an enhanced corrosion resistance due unhindered by films of insoluble corrosion products,
to the existence of a complex naturally-formed pro- is usually low. Nevertheless, although the breakdown
tective film which includes both aluminum oxide15 of a protective oxide film on copper is not likely to
and copper oxide. If damaged, the film is self healing lead to such rapid attack as with a more reactive
and this gives aluminum bronzes good wear, cavita- metal (e.g., aluminum), in practice the good behavior
tion, and antigalling characteristics. of copper, and, more particularly, of some of its alloys
often depends to a considerable extent upon the
3.07.1.1.8 Silicon–bronzes maintenance of a protective film of oxide or other
Silicon–bronzes usually contain 2.8–4.5% Si and insoluble corrosion product.
0.8–1.5% Mn. The wrought alloys combine high ten- In many environments, alloys of copper can be
sile strength (see Table 2) with good corrosion resis- more resistant to corrosion than is copper itself,
tance and an attractive color. They are used in chemical owing to the incorporation either of relatively corro-
equipment and marine hardware. The cast alloy has sion-resistant metals, such as nickel or tin, or of
found application in statuary, art castings, and plaques. metals such as aluminum or beryllium which would
1944 Non-Ferrous Metals and Alloys

be expected to assist in the formation of protective stable complex cuprous ion. Cuprous salts can there-
oxide films. Several types of copper alloys are liable fore exist in contact with water only if they are very
to undergo a selective type of corrosion in certain sparingly soluble (e.g., cuprous chloride) or are com-
circumstances, the most notable example being the bined in a complex, for example, [Cu(CN)2]
and
dezincification of brasses (see Section 3.07.3.3.2). [Cu(NH3)2]+. Cuprous sulfate can be prepared in
Some alloys are liable to suffer stress corrosion by nonaqueous conditions, but because it is not spar-
the combined effects of internal or applied stresses ingly soluble in water, it is immediately decomposed
and the corrosive effects of certain specific environ- by water to copper and cupric sulfate. The equilib-
ments. The most widely known example of this is the rium between copper and cuprous and cupric ion is
season cracking of brasses (see Section 3.07.3.6). In disturbed by the presence of oxygen in solution, since
general, brasses are the least corrosion-resistant of the reaction shown in eqn [3] is facilitated, the oxygen
the commonly used copper-based alloys. acting as an electron acceptor.
The various grades of commercial copper avail-
able do not differ to any marked extent in their
3.07.2.2 Behavior of Copper Electrodes
corrosion resistance, and a choice between them is
usually based on other grounds. Subsequent refer- The electrode potential behavior of copper in various
ences to the corrosion behavior of copper may there- solutions has been investigated in detail by Gatty and
fore be taken to apply broadly to all types of copper. Spooner.16 According to these workers a large part of
The choice of alloy for any particular application the surface of copper electrodes in aerated aqueous
is determined by the desired physical, mechanical, solutions is normally covered with a film of cuprous
and metallurgical properties. Within these limits, oxide and the electrode potential is usually close to
however, a range of materials is usually available. the potential of these film-covered areas. The filmed
It is essential that, at the very earliest stage, the metal simulates a reversible oxygen electrode at the
choice of materials and the detail of design of the oxygen concentration and pH, less an overvoltage
installation should be considered from the point of determined by the existing current density. The prin-
view of corrosion if the best performance is to be cipal factors which affect the electrode potential are
obtained in service. This is particularly true for thus the nature of the solution, the way in which this
copper alloys, where protective measures are not influences the area of oxide film, and the supply of
normally applied. oxygen to the metal surface. In solutions containing
chloride, there is a tendency for the establishment
3.07.2.1 Electrode Potential Relationships of the Cu/CuCl/Cl
electrode potential, so that
the activity of chloride ions is an important factor in
The electrode potentials for the equilibria: determining the electrode behavior. From a knowl-
Cu2þ þ 2e⇆Cu ½1 edge of the solubility products of cuprous chloride
Cuþ þ e⇆Cu ½2 and cuprous oxide, it is possible to predict under
Cu2þ þ e⇆Cuþ ½3 what conditions chloride or hydroxyl ions are the
potential-determining ions. According to Gatty
are þ0.34, þ0.52, and þ 0.17 V respectively, as and Spooner, chloride determines the potential if
measured against a standard hydrogen electrode. aOH
< 10
8:1  aCl
and hydroxyl determines the
For the equilibrium potential if aOH
> 10
8:1  aCl
. However, this will
2Cuþ ⇆Cu2þ þ Cu ½4 not hold in concentrated solutions as complex

2 [CuCl2]
ions as well as simple ions will be present.
Kc ¼ aCu2þ = aCu
2
þ
A further factor to be considered is the ready formation
Kc has the value of 1  106 at 298 K, and in solutions of insoluble basic compounds. In solutions which do not
of copper ions in equilibrium with metallic copper, contain chloride (e.g., sulfate or nitrate solutions), cor-
cupric ions therefore greatly predominate over rosion rates are usually lower and the electrode poten-
cuprous ions, except in very dilute solutions. Cupric tial is more steady over a wide range of conditions.
ions are therefore normally stable and become unstable Gatty and Spooner consider that the rate of cor-
only when the cuprous ion concentration is very low. rosion is probably determined by the rate at which
A very low concentration of cuprous ions may be metal ions can escape through pores in the protective
produced in the presence of a suitable anion, by the oxide film, and this is supported by the results of
formation of either an insoluble cuprous salt or a very
 Corrosion of Copper and its Alloys 1945

experiments on the anodic and cathodic polarization Hickling and Taylor19 and, more recently, by Kuksina
of copper. et al.20 using electrochemical methods which record
One of the potential–pH equilibrium diagrams the variation of potential with the Faradaic charge
devised by Pourbaix17 relating to the Cu–H2O system passed. In alkaline solutions, the main stages of
is shown in Figure 1. Such diagrams are of con- polarization have been found to be (1) the charging
siderable assistance in discussing many problems of the double layer, and (2) the formation of a film
associated with the chemistry, electrochemistry, elec- of cuprous oxide which was almost at once oxidized
trodeposition, and corrosion of copper. It must be to cupric oxide. Mayer and Muller21 report evidence
pointed out that the thermodynamic approach on that this converts to Cu2O3 at potentials above
which these are based has limitations, the most
25 mV versus Hg/HgO in 1 M KOH. However, in
important being that, although predictions can be 0.1 M NaOH,20 the Cu2O film was found to be
made about the possibility of a given reaction pro- around four molecules thick when oxygen evolution
ceeding in certain circumstances, no information can first commenced. In buffer solutions of decreasing
be gained about the rate at which it will proceed. pH, the formation of sparingly soluble salts pre-
A similar method of representing the behavior ceded or accompanied the formation of the oxide
of copper in dilute aqueous solutions by means of film. In acid solutions yielding soluble copper salts,
corrosion-current/pH diagrams has been given by no passivity developed, the anodic process being
Rubinic and Markovic.18 A study of the behavior of merely dissolution of copper. In nitrate solutions,
copper when anodically polarized has been made by the cathodic process has a significant effect on the

0 –2 –4
++
–6
–6 –4 –2 0
Cu 4⬘ 21
20
8⬘
9⬘

30

Cu2O3hydr
CuO2–

b 17
15
Cu++ 10⬘ 32
1⬘ 31
11⬘
–6 –4 –2 0
0 -2 –4 –6 26 CuO 19
23 18
HCuO2– CuO2–
22 5⬘
Cu+ Cu2O 14
12 27 28
6⬘ 3⬘ –2
25 –4
–6
Cu
a

7⬘

–2 0 2 4 6 8 10 12 14 16
pH
Figure 1 Potential–pH equilibrium for the system copper–water at 25  C.
1946 Non-Ferrous Metals and Alloys

anodic dissolution of copper. Low-frequency AC alloys involve roofing, plumbing, naval and commer-
polarization techniques have shown22 that OH
ions cial shipping, and desalination plant. The level of
adsorbed during the cathodic half-cycle facilitate corrosion and corrosion mechanisms occurring in
copper dissolution in the anodic half-cycle through different environments depend on the alloy group
the production of an insoluble hydroxide layer. Other chosen and can vary from mildly resistant to highly
workers have also studied the anodic behavior of resistant. Various corrosion mechanisms exist and
copper or copper alloys in alkaline23 and in acid24,25 these have been found to be related to the type of
solutions, using both static conditions and turbulent alloy and to the environment to which it is exposed.
conditions, such as those generated by rotating cylin- The following sections give details of the effects seen
der electrodes26 and the presence of light has been in a range of different corrosive environments
found to have an influence on the electrochemistry.21 experienced.
For instance, in Cu–Al–Sn anodically polarized in
sodium sulfate solution,27 an enrichment of the pas-
3.07.3.1 Atmospheric Corrosion
sive film with aluminum oxide can be detected as the
photocurrent spectrum changes from a ‘copper-type’ Copper has a high degree of resistance to atmo-
to an ‘aluminum-type’ with time. spheric corrosion and is widely used for roofing
The excellent corrosion resistance of cupronickel sheets, flashings, gutters, and conductor wires as
alloys is related to the formation of a particularly well as for statues and plaques. The corrosion resis-
effective protective film of corrosion products in the tance of copper and its alloys is due to the develop-
early stages of exposure. A number of studies have ment of protective layers of corrosion products,
been carried out involving a wide range of analytical which act to reduce the subsequent rate of attack.
techniques.28 The film formed is dark brown in color The formation, in course of time, of the typical green
and there is general agreement that it contains an ‘patina’ gives copper roofs a pleasing appearance;
inner layer of Cu2O which is enriched with nickel indeed, methods are used to produce it artificially
and iron. Recent electrochemical studies29 have iden- or to accelerate its formation.31 The nature of the
tified that over this layer, a thin outer layer of CuO corrosion products formed on copper exposed to the
develops and an increasing nickel content in the alloy atmosphere has been exhaustively studied by Vernon
produces a decrease in the overall corrosion rate. The and Whitby.31–33 A comprehensive review of the lit-
corrosion rate also falls as the chloride ion concen- erature on atmospheric corrosion including copper
tration rises above 0.3 M due to an enhanced forma- and copper alloys up to 1995 has been produced by
tion of the passive Cu2O film.30 On this subject, in a Dechema34 It has been found that in the early periods
seawater context, see Section 3.07.3.5. of exposure, the corrosion deposit contains sulfide,
oxide, and soot. By the action of sulfuric acid and by
the oxidation of sulfide, copper sulfate is formed and
3.07.3 Corrosive Environments this hydrolyzes and forms a coherent and adherent
Experienced basic form of this compound. Initially, this approxi-
mates to CuSO4–Cu(OH)2 but it gradually increases
Copper and its alloys have a very diverse range of in basicity until after 70 years or so it becomes
properties and their application exposes them to CuSO4–3Cu(OH)2 and is identical with the mineral
many types of environment. Artifacts dating back brochantite. In some cases, small quantities of basic
thousands of years are testimony to the resilience of carbonate, CuCO3–Cu(OH)2 (malachite), are also
copper alloys to atmospheric corrosion, waters, and present, and, near the sea coast, basic chloride
soils. Also, they have been recognized for marine use CuCl2–3Cu(OH)2 (atacamite) is produced. However,
for several decades and are still selected even though even very near the sea coast, sulfate usually predo-
other noncopper alloy systems have been developed minates over chloride.
in the interim. The release of copper ions and the In laboratory tests, Vernon33 showed that the rela-
cuprous oxide film have antifouling properties and, in tive humidity and the presence of sulfur dioxide have
addition, recent work has proved their antimicrobial a profound effect on the rate of corrosion of copper,
properties; investigations into the mechanisms for as they do with many other metals. He found that
these beneficial effects are ongoing, as are their when the relative humidity was less than 63%, there
development into new applications. More traditional was little attack even in the presence of much sulfur
applications requiring corrosion resistance of copper dioxide, but when the relative humidity was raised to
 Corrosion of Copper and its Alloys 1947

75%, corrosion became severe and increased with the tested behaved very similarly except for the brasses,
concentration of sulfur dioxide present. By exposing which deteriorated more rapidly owing to dezincifi-
specimens to the atmosphere at different times of the cation (see Section 3.07.3.3.2). Several series of
year, Vernon found that the rate of attack on copper atmospheric exposure tests have been carried out
was determined by the conditions prevailing at the since Hudson’s work, and the loss in weight data
time of first exposure. For specimens first exposed in obtained in six of the most important investigations
winter, there was a linear relationship between are summarized in Table 5. In all cases, losses in
increase in weight and time of exposure, indicating tensile strength were also determined, and the results
that the layer of corrosion product formed under from the two methods were, in general, in good
these conditions was nonprotective. For specimens agreement. However, for alloys suffering selective
first exposed in summer, the square of the increase attack (such as with the dezincification of brasses)
in weight was proportional to the time of exposure. change in mechanical properties usually provided a
This indicated that the coating formed in summer more reliable indication of deterioration than weight
(when the atmospheric pollution was relatively low) loss. Some other findings common to all the tests
was protective. It was found that the parabolic law were that (1) corrosion rates decreased with time,
holds when the corrosion product layer obstructs the (2) least attack occurred at rural sites and most in
access of the corrosive agent to the metal, the rate of urban and industrial atmospheres, (3) corrosion was
attack then being inversely proportional to the thick- uniform, and (4) with a few exceptions, there was no
ness of the layer. It was apparent that the protective significant pitting.
character of the layer persisted through subsequent Tracy et al.36 exposed specimens of 11 different
periods when the pollution was relatively high. grades of copper in the form of sheet and wire to
Copper tarnishes rapidly when exposed to atmo- rural, marine, and industrial atmospheres in the
spheres containing hydrogen sulfide. Atmospheric United States for periods up to 20 years. The differ-
corrosion tests on copper and several copper alloys ences in the behavior of the materials were small and
were carried out by Hudson35 at a number of sites in of little, if any, practical significance. Very similar
the United Kingdom. Corrosion damage was assessed results for various types of copper were found by
by one or more of the following methods: gain in Mattsson and Holm37 in Sweden and Scholes and
weight, loss of weight after cleaning, loss of electrical Jacob38 in the United Kingdom (see Table 5).
conductivity, and loss of tensile strength. Hudson Table 5 gives the results of tests on copper alloys
found that the resistance to atmospheric corrosion by Tracy,36 Thompson,40 and Mattson and Holm,37
was high and that the rate of attack tended to de- Scholes and Jacob38 and, more recently, Morcillo39
crease with time of exposure. Little difference was together with their co-workers. The tests of Tracy
found between the behavior of arsenical copper and and Scholes were for periods up to 20 years; in the
high-conductivity copper, and most of the alloys work of Thompson and Mattson, specimens were

Table 5 Atmospheric corrosion tests on copper and copper alloys

No. of types of No. of different No. of Period of Average rates of attack from
copper alloys sites exposure weight losses (mm year
1  104)
(years)
Rural Marine Urban/
sites sites Industrial
sites

Tracy, Thompson, 11 – 4 20 5.6–4.3 6.9–9.4 8.6–12

and Freeman36
Tracy43 2 9 7 20 0.5–7.6 1.3–23a 13–30a
Thompson40 1 17 4 7 3.3–10 4.3–25 13–27
Mattson and 4 – 3 7 5–6 7–8 10–12
Holm41 – 18 3 7 2–5 6–11 9–22
Scholes and 4 – 2 20 – 6–10 11–20
Jacob38 – 17 2 20 – 8–26 14–38
Morcillo et al.39 1 – 66 4 0.1–0.2

Rates of attack for high tensile brass were (45–115)  10
4 mm year
1.
a
1948 Non-Ferrous Metals and Alloys

removed after 2 and 7 years and further specimens correlations of weight increase with other atmo-
were removed after 16 years.41 The average penetra- spheric species was not found to be possible. How-
tion during the 16-year period was found to be about ever, other works report that the corrosion of copper
the same as during the first 7 years, but considerably by sulfur dioxide is measurably accelerated by the
lower than during the initial 2 years. The materials presence of NO245 or ozone.46 The recent study
tested included brass, nickel–silvers, cupronickels, conducted in South America, which involved the
copper–beryllium alloys, and various bronzes. Recent comparison of 21 unpolluted sites with 45 marine
studies have involved the investigation of seasonal locations, showed that there is a threshold chloride
effects of industrial pollutants (NOx) and comparison concentration of 20 mg m
2 day
1 in the environ-
of rural and marine locations in South America.42 ment above which the corrosion rate intensifies.
In the tests described by Tracy,43 a high-tensile Other recent studies have involved comparing the
brass suffered severe dezincification (see Table 5). effects of different types of climates throughout four
The loss in tensile strength for this material was continents.47
100% and, for a non-arsenical 70–30 brass, 54%; no From the work described and other investiga-
other material lost more than 23% during 20 years’ tions,48 it is evident that copper and most copper
exposure. In Mattsson and Holm’s tests, the highest alloys are highly resistant to atmospheric corrosion.
corrosion rates were also shown by some of the brasses. The reported results indicate that copper itself is as
Dezincification caused losses of tensile strength of up good as, or better than, any of the alloys with regard
to 32% for a b brass and up to 12% for some of the to atmospheric corrosion. Some of the brasses are
a–b brasses; no other materials lost more than 5% in liable to suffer rather severe dezincification and it is
7 years. Dezincification also occurred, though to a unwise to expose these to the more corrosive atmo-
lesser degree, in the a brasses tested, even in a material spheres without applying some protection.
with as high a copper content as 92%. Incorporation of When unusually rapid corrosion of copper and its
arsenic in the a brasses consistently prevented dezin- alloys occurs during atmospheric exposure, it is likely
cification only in marine atmospheres. to be for one of the following reasons:
In Thompson’s reported work, the alloy showing
1. Extreme local pollution by products of
the lowest rate of attack at all sites was a bronze
combustion.
containing 7Al–2Si. Relatively high corrosion rates
2. Bad design or construction, for example, the pres-
were shown by Cu–5Sn–0.2P at a marine site and
ence of crevices where moisture may lodge for
Cu–2.5Co–0.5Be in an industrial environment. The
long periods, including, for instance, coiled wire.49
beryllium–copper alloys were the only materials
3. Constant dripping of rain water contaminated by
to show measurable pitting, the deepest attack
atmospheric pollution (e.g., from near-by chimney
being 0.6 mm after 7 years. In Scholes and Jacob’s
stacks) or by organic acids from lichens, etc.
tests pitting, intergranular (or transgranular) penetra-
4. Corrosion fatigue due to inadequate allowance for
tion, or selective attack occurred on some alloys.
expansion and contraction with consequent buck-
The maximum depth of attack exceeded 0.2 mm in
ling as the temperature fluctuates.
20 years on 6 of the 21 materials (three brasses, two
nickel silvers, and Cu–20Ni–20Mn), but exceeded Most of these disorders can be avoided by attention
0.5 mm in 20 years only on Cu–20Ni–20Mn and to design.50
60/40 brass. These two latter alloys lost up to 73% The discussions in recent years of the possibility
and 13% respectively of their tensile strength; no of pollution occurring as a result of released copper
other alloys lost more than 10% in 20 years. due to atmospheric corrosion have resulted in studies
The work of Ramos et al.42 has demonstrated a of runoff from roofs and facades by several work-
clear correlation between seasonal increases in SO2 ers.51–54 A number of research results have been
and NOx concentrations in urban atmospheres with published by the Royal Institute of Technology,
higher corrosion rates and the presence of sulfates Stockholm, Sweden55–61 and the EMPA laboratories,
in the corrosion products. This broadly agreed with Switzerland. It has been found that, after a short
a previous study of comparative weight gains of cop- initiation period, the runoff rate of copper per year
per over a 2-year period at 39 sites spread across is constant over a long time.55,56,58,62 This makes it
Europe,44 where a clear correlation was found possible to model the copper runoff rate, R,57 based
between weight gain and SO2 content of the environ- on SO2 concentration, the pH of the rainwater, and its
ment, although attempts to find mathematical quantity. The roof surface angle of inclination Y has
 Corrosion of Copper and its Alloys 1949

also been taken into account,61 according to the fol- compared with the runoff from a roof prepatinated
lowing equation: 40 years ago, which was found to have a copper
ðcos YÞ runoff rate which was 10% lower.
R ¼ ð0:37½SO2 0:5 þ0:95½Rain10
0:62pH Þ ½5
ðcos 45 Þ
3.07.3.2 Soil Corrosion
The seasonal variation of copper corrosion rate and
the runoff rate have also been studied.60 Several extensive series of soil-corrosion tests have
Some workers note that the released metal from been carried out by the National Bureau of Standards
the corrosion reaction is in ionic form directly on the in the United States, and the results summarized by
roof and the environmental impact of these released Romanoff.65 In one series, 2 types of copper and 10
ions has been determined. Other workers state that copper alloys were exposed in 14 different soils for
the run-off is mainly in particulate form. However, periods up to 14 years. The results for the copper
the interaction with solid surfaces in the near vicinity specimens are summarized in Table 6.
of buildings has been looked at together with the The behavior of the phosphorus-deoxidized and
changes of transport which occur from the source to tough-pitch coppers was, in general, very similar. At
the end product. Investigations of reactivity have the less corrosive sites, with a few exceptions, copper
been made toward various natural and manmade was the best material. Most of the alloys lost weight
surfaces, such as different soil systems, limestone, ranging up to twice that of copper, with maximum
and concrete. The results illustrate that, for scenarios depths of attack up to three times greater. At the
where copper ions come in extensive contact with other sites, although the coppers were usually rather
solid surfaces, a large fraction of released copper is better than the alloys, some of the alloys were occa-
retained in the immediate vicinity of the building.56 sionally superior.
The potential ecotoxic effects from released copper The three most corrosive sites were rifle peat
have also been investigated. Copper biosensor testing (pH 2.6), cinders (pH 7.6), and tidal marsh (pH
with a bacteria and growth inhibition testing with 6–9). Corrosion of some of the alloys was particularly
green algae have been used. The runoff water directly severe in the cinders. The behavior of the brasses
after release was found to cause significant reduction tested, particularly those high in zinc, was rather dif-
of the green algae growth rate, indicating that the ferent from that of the other materials. In most cases
copper is bioavailable. However, it was found that dezincification occurred and the brasses were the
contact with solid surfaces effectively reduces this worst behaved materials; in the cinders, for instance,
bioavailable copper. several brass specimens were completely destroyed by
The fate of released copper in runoff has also been dezincification. However, in some of the soils rich in
studied in the United States.62–64 The results sulfides, the brasses were the best materials.
obtained also show that the bioavailable copper frac- The British NonFerrous Metals Research Associ-
tion is low after contact with solid surfaces. ation carried out two series of tests, the results of
Sundberg62 followed the runoff from a new copper which have been given by Gilbert66 and Gilbert and
roof for 3.5 years. A relatively stable runoff rate per Porter67; these are summarized in Table 6. In the first
year was found after 0.5 years. The result was series,66 tough pitch copper tubes were exposed at

Table 6 Soil-corrosion tests on copper by National Bureau of Standards and British Nonferrous Metals Research
Association (BNFMRA)

Period of Average rate of attack Maximum rate of

exposure (years) from loss in weight pitting (mm year
1)
(mm year
1  10
4)

BNFMRA first series five least corrosive soils 10 0.5–2.5 Nil

BNFMRA second series four least corrosive soils 5 5.0–25 0.140
Nat. Bur. Standards nine least corrosive soils 14 4.0–25 0.043
Nat. Bur. Standards two next most corrosive soils 14 23–130 0.033
BNFMRA first series acid clay and acid peat 10 53–66 0.046
BNFMRA second series cinders 5 66 0.32
Nat. Bur. Standards three most corrosive soils: rifle 14 160–355 0.115
peat, cinders, tidal marsh
1950 Non-Ferrous Metals and Alloys

seven sites for periods of up to 10 years. The two Ammonium and sulfide species appear to be rela-
most corrosive soils were a wet acid peat (pH 4.2) tively benign. The corrosion products which result
and a moist acid clay (pH 4.6). In these two soils, are cuprite and malachite, the latter being favored for
there was no evidence that the rate of corrosion was soils with higher water content.70
decreasing with duration of exposure. In the second
series,67 phosphorus deoxidized copper tube and sheet
were exposed at five sites for 5 years. Severe corrosion 3.07.3.3 Corrosion in Natural Waters
occurred only in cinders (pH 7.1). In these tests, sul-
Copper and copper alloy pipes and tubes are used in
fides were found in the corrosion products on some
large quantities both for conveying fresh and salt
specimens and the presence of sulfate-reducing bacte-
water and in condensers and heat exchangers where
ria at some sites was proved. However, it was not clear
fresh or salt water is used for cooling. Pumps, screens,
to what extent the activity of these bacteria was a factor
valves, and other ancillary equipment may also be
accelerating the corrosion of copper.
largely constructed of copper alloys. Large tonnages
Cinders and acid peaty soils are obviously among
of these materials are therefore used on offshore struc-
the soils most corrosive toward copper. There is,
tures, multistage flash desalination plants, power sta-
however, no direct relationship between the rate of
tions, on board ships, in sugar factories, and in oil
corrosion and any single feature of the soil composi-
refineries, as well as in hot and cold water circuits
tion or constitution.68 For instance, in the American
and heating and cooling systems in hospitals, factories,
tests, corrosion in several soils with either low pH or
hotels, and homes.
high conductivity was not particularly severe, while
Corrosion problems that arise frequently are dis-
the British tests show that chloride or sulfate contents
cussed under separate headings, depending on whether
are not necessarily harmful. The latter tests showed
the environment is seawater or freshwater. In fact, there
that bare copper can safely be buried in a wide range
is no sharp dividing line between these environments,
of soils without fear of excessive corrosion. Experi-
since some harbor, estuarine, and brackish well waters
ence of the behavior of copper water service pipes,
are mixtures of seawater and freshwater and are often
which are used widely, confirms this. Difficulties are
variable in composition. Corrosion has been found to
generally confined to ‘made-up’ ground containing
occur in all these media, particularly in seawater, but
cinders, etc. and a few other aggressive soils, and in
this is more frequently seen as a result of poor design or
these circumstances it is necessary to apply protec-
operation than as a result of lack of materials suitable
tion such as bitumen-impregnated wrappings or plas-
for the application. This section will deal with the types
tic coatings. Tin coatings cannot be recommended as
of corrosion which can be seen in all types of natural
experience shows that accelerated attack is liable to
water; seawater, brackish water, or freshwater. Separate
occur at pores and scratches in the coating, leading to
sections will follow which deal with corrosion types
premature failure. Copper water pipes have been
seen almost entirely solely in freshwater and with the
known to fail by the action of stray electric currents,
behavior of copper alloys specifically in seawater.
but this is not a common occurrence.
There is agreement between the soil-corrosion
tests carried out by National Bureau of Standards 3.07.3.3.1 Impingement attack
and practical experience of the behavior of hot- Copper alloys have good corrosion resistance under
pressed brass fittings used for joining copper water moderate fluid flow rates. However, above a certain
service pipes. These duplex-structure brass fittings flow velocity, called the breakaway velocity, the shear
are liable to suffer attack by dezincification in many stress of the liquid on the alloy protective surface film
soils in which copper behaves satisfactorily, and, for is sufficient to damage it and much higher corrosion
burial underground, fittings of copper, gunmetal, or rates occur. This phenomenon is called impingement
dezincification-resistant brass are to be preferred. attack or erosion–corrosion. Therefore, tube and pip-
In general, it may be said that, unless there is some ing systems are designed to operate satisfactorily up
special reason for using a copper alloy, it is preferable to a maximum velocity and it is important that this is
to choose copper for applications involving sub- not exceeded in service. Breakaway velocity can be
terranean service. A comparison of the corrosion influenced by many factors, including the alloy being
produced through the influence of possible ionic used, the resilience of the surface film, the geometry
species present around buried copper has shown69 of the product and system, the corrosive nature of the
that the major damage is caused by chloride ions.
 Corrosion of Copper and its Alloys 1951

fluid being handled, pollution, solids (e.g., sand in or a combination of the following: reducing the pump
seawater), and turbulence.71 output, increasing the pipe size, modification of the
Copper tubes have been found to suffer from change of direction to one which is less abrupt, open-
impingement attack in systems where the speed of ing partially closed valves, etc. The maximum flow
water flow is unusually high. The phenomenon has velocity quoted in European Standard EN806 part 3
been discovered to be dependent in some degree on is 2.0 m s
1 for header, riser, and floor service pipes
the quality of the water, for instance where no pro- and 4.0 m s
1 for (replaceable) connection pipes to
tective scale is able to form, for example, in a soft one fitting. The Swedish Building Standard 2522
water containing appreciable quantities of free car- recommends a reduction in velocity as the design
bon dioxide.72 Impingement attack is most often seen operating water temperature increases viz, 2 m s
1
downstream of poorly installed fittings or sharp at 10  C, 1.5 m s
1 at 50  C, 1.3 m s
1 at 70  C, and
bends in pipework systems. Such obstructions to 1.0 m s
1 at 90  C.
flow and sharp changes in direction where the speed The actual velocity at which impingement com-
of the water is high can lead to eddy currents con- mences depends on the fluid and varies from alloy to
centrating the flow on specific parts of the tube, alloy.74 In general, the nickel aluminum bronzes and
the creation of bubbles at areas of low pressure copper–nickel alloys have the highest velocity toler-
(which subsequently collapse), and the streaming of ances in seawater and are somewhat better than gun-
particulate matter. The latter can act alone or in metals, brasses and tin bronzes75 (see Table 7 and
concert to remove any protective scale that has Section 3.07.3.5). The cupronickel 90–10 and 70–30
formed on the copper surface, thus exposing the alloys are commonly used for seawater condensers,
metal to further corrosion and subsequent removal heat exchangers, and pipework in naval vessels as well
of corrosion product. In such a way, severe metal loss as merchant shipping. For tube sizes used in heat
can occur, leading eventually to failure of the tube. exchangers and condensers, the velocity is limited
Impingement attack is characterized by areas of to 2–2.5 m s
1. For seawater pipework of internal
bright metal and horseshoe-shaped undercut areas, diameter 100 mm and with bends of long radius, the
their direction being as though the horse was walking recommended maximum seawater flow velocities are
upstream. In the middle of such undercut areas, there 3.5 m s
1 for the 90–10 alloy and 4 m s
1 for the 70–30
may be islands of bright metal or metal still retaining alloy76. This has worked well in practice although it is
some protective corrosion product. An example of now believed to be a little on the conservative side.77,78
this phenomenon is shown in Figure 2. Ball valve Areas causing high turbulence such as bends with tight
seatings may also suffer an erosive type of attack. The radiuses, partially throttled valves, and partial obstruc-
corrosion of ball valves, including the effect when the tions need to be avoided.
water is chlorinated, has been studied by several Other cupronickel alloys have been developed and
workers.73 Avoidance of impingement attack is usu- have been found to offer even better resistance to
ally achieved by reducing the flow velocities by one impingement attack. In particular, a 16.5% Ni–0.5%
Cr alloy first developed by INCO in the 1970s has a
much higher, critical shear stress than the 70–30
alloy.12 Also a 2% Mn–2% Fe–30% Ni alloy, devel-
oped for extra impingement resistance in situations
where entrained sand is present in seawater, is now
successfully used in the more demanding areas of
desalination plants.9
Gunmetals and aluminum bronzes have good
resistance to impingement attack but these alloys
are not normally used for heat exchange tubing, the
former because they are casting alloys and the latter
because it may pit in quiescent conditions. However,
both groups are used for components such as pumps
and valve bodies. The nickel aluminum bronze alloy
Figure 2 Photograph showing typical impingement attack
caused by eddy currents which were present as a result of is used for propellers and pump components as it has
burrs on the internal wall. The tube type is 15 mm diameter excellent resistance to cavitation compared to many
copper tube to EN 1057, R250 (half-hard condition). other copper based alloys.
1952 Non-Ferrous Metals and Alloys

Table 7 Comparative results showing corrosion and erosion/corrosion performance of a number of copper alloysa

Alloy General corrosion Crevice corrosion Minimum flow rate to produce

rate (mm year
1) b rate (mm year
1) b erosion/corrosion (m s
1) c

Wrought Alloys:
Phosphorus deoxidized 0.04 <0.025 1.8
copper, CW024A
Admiralty brass, CW706R 0.05 <0.05 3
Aluminum brass, CW702R 0.05 0.05 4
Naval brass, CW712R 0.05 0.15 3
HT brass, CW705R 0.18 0.75 3
90–10 cupronickel 0.04 <0.04 3.6
70–30 cupronickel 0.025 <0.025 4.5
5% Al–bronze 0.06 <0.06 4.3
8% Al–bronze 0.05 <0.05 4.3
9% Al–bronze 0.06 0.075 4.5
Nickel aluminum bronze 0.075 <0.30 4.3
Aluminum silicon bronze 0.06 <0.075 2.5
High strength cupronickel 0.02 <0.02 4.8
(Cu–Ni–Al–Mn–Fe)
Cast alloys:
Gunmetal, CC491K 0.04 <0.04 3.6
Gunmetal, CuSn10Zn2 0.025 <0.025 6
High tensile brass, CC765S 0.18 0.25 2.5
Aluminum bronze, CC331G 0.06 <0.06 4.5
Nickel aluminum bronze, 0.06 <0.5 4.3
CC333G
Manganese aluminum 0.04 3.8 4.3
bronze, CC212E

a
Due to difficulties of achieving consistent results for tests in seawater, data should be used for comparing relative performance rather than
being taken as absolute.75
b
The figures for general corrosion rate and crevice corrosion rate were determined using samples fully immersed beneath rafts in
Langstone Harbour, Portsmouth, UK, for 1 year.75
c
The corrosion/erosion resistance tests were carried out using the following method (known as the Brownsdon and Bannister method): the
specimens were fully immersed in natural sea water and supported at 60  C to a submerged jet, 0.4 mm diameter placed 1–2 mm away,
through which air was forced at high velocity. From the minimum air jet velocity required to produce corrosion/erosion in a fourteen-day
test, the minimum sea water velocity required to produce corrosion/erosion under service conditions was estimated on the basis of known
service behavior of some of the materials.

A number of studies have evaluated the impinge- 3.07.3.3.2 Dezincification of brasses

ment resistance for marine condensers and piping Historically, the most common dealloying phenome-
involving several types of test apparatus, including non seen in copper alloys has been the dezincifica-
rotating discs, rotating spindles, model condensers, tion of brasses. In recent years, the development
multivelocity jet tests, and jet impingement tests.79 of dezincification-resistant brasses and a greater
This work has proved reliable in ranking materials as understanding of the required conditions under
a function of impingement resistance and has been an which dezincification manifests itself have lessened
important factor in the development of alloys resis- its occurrence, but it retains a high degree of scien-
tant to impingement attack. tific interest. Dezincification is characterized by
Experience has shown that for intermittent regions of the brass becoming replaced by a porous
flow (as might be the case of firewater systems used mass of copper which, though retaining the shape of
on offshore platforms which are tested periodically), the original article, has virtually no strength. There
short-term high velocities in the order of 7–15 m s
1 has long been discussion as to whether there is selec-
for cupronickels are not detrimental. Also open geo- tive corrosion of the zinc in the brass, which leaves
metries need not have the velocity restrictions of pipe the copper behind, or whether complete dissolution
and tubing; for example, 90–10 cupronickel has been of the brass occurs, followed by redeposition of cop-
successfully used on ship hulls operating at 24 knots per. Possibly both processes occur under different
(12 m s
1) with little thinning experienced.9 circumstances.
 Corrosion of Copper and its Alloys 1953

The mechanism of dezincification of brass has but not in a–b brasses. An interesting observation is
been investigated and discussed by Evans,80 Fink,80 that the presence of a small impurity content of
Lucey,81 Feller,82 and Heidersbach,83 and is referred magnesium will prevent arsenic in a brass from hav-
to in many other papers.84–92 Recent extensive stud- ing its usual inhibiting effect.102
ies93,94 which have investigated the distribution of The addition of antimony or phosphorus, in
copper isotopes and the effects of specimen rotation amounts similar to arsenic, are claimed to be also
during testing, show that redeposition of copper is a capable of preventing dezincification of a brasses.
major mechanism. However, most manufacturers use arsenic. It appears
With a single-phase brass, the whole of the desirable to avoid using phosphorus, as Bem103 has
metal in the corroded areas is affected. Dezincifica- shown that this element can, in some circumstances,
tion may proceed fairly uniformly over the surface, lead to an undesirable susceptibility to intergranular
and this ‘layer type’ takes much longer to cause corrosion. The same can be true for arsenic additions
perforation than the more localized ‘plug type’ over 0.05%.
which more often occurs.95 With a two-phase brass, A dezincification resistant alloy, CW602N, was
the zinc-rich b phase is preferentially attacked and first introduced in 1980. This alloy is a leaded brass
eventually the a phase may be attacked as well. The with a zinc content sufficiently high to permit hot
zinc corrosion products which accompany dezincifi- forging and extrusion in the b range without crack-
cation may be swept away, or, in some conditions, ing. After hot working, a heat treatment of up to 6 h at
may form voluminous deposits on the surface. 500  C followed by slow cooling transforms any
These may in turn lead to blockages, for example, residual b phase to a so that the finished component
in fittings. In general, the rate of dezincification is essentially a brass. Dezincification is inhibited by
increases as the zinc content rises, and great care adding arsenic (0.02–0.15%) which protects the
needs to be exercised in making brazed joints with a phase, and good machinability is assured by adding
copper/zinc brazing alloys, particularly if they are to lead (1.7–2.8%). The impurities iron and manganese,
be exposed to seawater. Under these conditions, a which combine with arsenic, must be carefully con-
properly designed capillary joint may last for some trolled for the arsenic to be effective. A rule of thumb
time, but it is preferable to use corrosion-resistant is that the percentage of arsenic must be greater than
jointing alloys such as silver solders96, as specified in the combined percentage of iron and manganese to
BS EN 1044:1999. provide resistance to dezincification. There is practi-
Factors which cause increased rates of dezincifica- cal evidence that the maximum limits for iron and
tion are high temperature, high chloride content of manganese allowed in the specification (0.1% each)
water, and low water speed.97–100 Dezincification is are too high as, at these levels, the arsenic may be
also likely to occur preferentially beneath deposits of rendered ineffective.
sand or silt on the metal surface, or in crevices where Newer studies of intergranular corrosion attack
there is a low degree of aeration. (IGA) of arsenic-containing dezincification resistant
Addition of 0.04% arsenic will inhibit dezin- brass93,104 show that there is a close relationship with
cification of a brasses in most circumstances and the degree of precipitation of iron–arsenic com-
arsenical a brasses can be considered to be immune pounds in the grain boundaries. The precipitates are
to dezincification for most practical purposes.101 formed during low temperature heat treatment or
There are conditions of exposure in which dezincifi- slow cooling after hot forging or a prior heat treat-
cation of these materials has been observed, for ment. Sulfide corrosion and dezincification in the
example, when exposed outdoors well away from grain boundary appear to be the result as the arsenic
the sea37 or when immersed in pure water at high is bound to impurities like iron. IGA has also been
temperature and pressure, but instances are rare. In reported for aluminum brass (CW 702R) and Mazza
other conditions, for example, in polluted seawater, and Torchio105 have presented a laboratory test
corrosion can occur with copper redeposition away method to reveal IGA in this material. The method
from the site of initial attack, but this is not truly has also been used successfully for dezincification
dezincification, which, by definition, requires the resistant brass104 and correlation with field tests in
metallic copper to be produced in situ. The work of seawater is good.
Lucey81 goes far in explaining the mechanism by The addition of 1% tin can markedly reduce the
which arsenic prevents dezincification in a brasses rate of dezincification in two phase brasses, and naval
1954 Non-Ferrous Metals and Alloys

brass (61Cu–38Zn–1Sn) is attacked considerably 3.07.3.3.4 Deposit attack and pitting

more slowly than 60/40 brass in seawater, although When water speeds are low and deposits settle on the
there may be virtually no difference between them in surface, pitting in copper and copper alloys is liable to
most freshwaters. Some of the cast complex high- occur by differential aeration effects. This is particu-
strength two-phase brasses containing tin, aluminum, larly so at water speeds below 1 m s
1. In seawater
iron, and manganese appear to have relatively good systems, such attack may occur under dead barnacles
resistance to dezincification, but they are by no or shellfish, the decomposing organic matter assisting
means immune to it. the corrosion process. Pitting is most likely to occur in
Dezincification of brasses in drinking water may polluted in-shore waters, particularly when hydrogen
occur, particularly in stagnant or slowly-moving sulfide is present. In such contaminated waters, non-
warm or hot waters relatively high in chloride and protective sulfide scales are formed and these tend to
containing little carbonate hardness.106 Dezincifica- stimulate attack. It has been found possible to develop
tion of a brasses is inhibited by the usual arsenic a mathematical model which can be successfully used
addition, but two-phase brasses are liable to severe to calculate the electrode potential below which cop-
attack in some waters. In such cases, dezincification- per is immune to pitting in tap water or seawater in the
resistant brass or gunmetal fittings should be used. If temperature range 25–75  C.112 Of the 26 ionic spe-
copper/zinc brazing alloys are used, these may dezin- cies which have been included in the calculation,
cify in water known to support this type of corrosion CO2
2

3 and SO4 were found to be the most aggressive.
and may consequently give rise to leaks.106
3.07.3.4 Corrosion in Freshwater
3.07.3.3.3 Selective attack in other alloys
Freshwaters are, in general, less corrosive toward
Selective attack analogous to dezincification can
copper than is seawater and copper is widely and
occur in other copper alloys, particularly in alumi-
satisfactorily used for distributing cold and hot waters
num bronzes and, less frequently, in tin bronzes,107
in domestic and industrial installations.113–116 Cop-
cupronickels,108 and other alloys. Dealuminification
per and copper alloys are used for pipes, hot-water
of aluminum bronzes has been studied extensively109
cylinders, ball valves, taps, fittings and heater sheaths.
and the results indicate that, while a-phase alloys
In condensers and heat exchangers using freshwater
suffer such attack comparatively rarely, alloys of
for cooling, tubes of 70/30 brass or Admiralty brass
higher aluminum content can be more susceptible.
are usually used, and corrosion is rarely a problem.
The electrochemical relationships are such that pref-
Nevertheless, the widespread use of copper and cop-
erential corrosion of the second phase is liable to occur
per alloys since the early part of last century espe-
in a–g2 alloys, but a–b alloys are relatively resistant to
cially in domestic water systems has meant that all
attack. Retention of b phase is favored by rapid cooling
adverse situations have been experienced and the
after casting or after high temperature heat treatment,
following are rare but notable corrosion issues. Two
and also by incorporating manganese in the alloy.
British Standards give guidance on the likelihood of
A tempering heat treatment in the temperature range
corrosion in water distribution and storage systems
of 650–740  C has been found to hinder the occur-
and in water recirculating systems. These are BSEN
rence of dealuminification due to the transformation
12502:2004 and BSEN14868:2005.
of the more corrosion-prone b phase to a combination
of a phase and comparatively benign k phases.110
3.07.3.4.1 Pitting
The addition of nickel to aluminum bronze has
Occasionally copper water pipes fail prematurely by
been found useful in controlling the occurrence of
pitting. This a general term and is used for any failure
the g2 phase, which has a corrosion potential
of the pipework system leading to a leak. Pitting
100 mV less noble than the a phase, thereby under-
corrosion of copper in drinking water systems is
going selective attack in seawater. Weill-Couly and
often categorized as Type I, II, or III but other
Arnauld111 have determined an empirical relationship,
types of localized corrosion are also known. However,
eqn [6] shown below, which denotes the aluminum
there may be no strict limits between Type I and
content of nickel–aluminum bronze castings below
Type II pits; in relatively saline tap waters, corrosion
which a resistance to dealuminification is found.
pits showing traits of both types have been found.
Ni Only through proper investigation can the cause of
Al  8:2þ ½6
2 pitting be identified, such as in the following sections.
 Corrosion of Copper and its Alloys 1955

3.07.3.4.1.1 Carbon film pitting pitting cannot proceed even in tubes containing car-
Carbon film pitting, also known as ‘Type I’ pitting, bonaceous cathodic films. He proposed that this is
has been a frequent problem. An example of this in a most probably due to the presence of small amounts
copper tube from a domestic water supply is shown of a naturally-occurring inhibitor in the water, proba-
in Figure 3 with the corrosion products removed bly an organic colloidal material, which stifles pitting
from the main pit. The characteristics of the pits are of copper. Pipe failures therefore only occur in waters
hemispherical cavities with large crusts of corrosion which contain little or none of this inhibitor.
products outside. The composition of the crusts is Pitting problems also occasionally occur in copper
mainly basic cupric carbonates for example, mala- water cylinders123 and, as a result of a study of this pro-
chite. Cuprous chloride and reddish cuprous oxide blem, Lucey117 has made suggestions about the mech-
crystals may be found inside the cavity. The presence anism of pitting of copper in potable water supplies.
of CaCO3 in the crust outside the cavity led Lucey117 Several suggested methods of avoiding pitting failures
to propose a particular mechanism for this type of in copper cold-water tubes have been evaluated.124–126
pitting. Contrary to conventional descriptions of the
pitting processes, Lucey postulated that the cathodic 3.07.3.4.1.2 Hot soft water pitting and Type II
reaction that is, the oxygen reduction, takes place at pitting
the crust of corrosion products which cover the cav- In hot water pipes, failures sometimes occur in cer-
ity. The phenomenon was found to occur in organi- tain areas supplied with soft waters from moorland
cally pure, cold waters originating from deep wells gathering grounds. The waters concerned contain a
and boreholes and was shown by Campbell118 to be few hundredths of a part per million of manganese,
associated with residual films of carbon on the bore of and in the course of several years’ exposure, a deposit
the tubes. This carbon was caused by decomposition rich in manganese dioxide is laid down in the hottest
of residual drawing lubricant during bright (reducing parts of the system. This may cause pitting which
atmosphere) annealing. It is therefore necessary for could eventually lead to failure.
manufacturers to take steps to avoid these harm- Hot-water pitting of another type, often referred
ful residues. This type of pitting attack has been to as ‘Type II’ pitting, is sometimes experienced in
identified in many different countries119 and may be soft waters having high sulfate content in relation
assisted by iron-rich precipitates which can be pres- to the carbonate hardness and a relatively low pH
ent at the grain boundaries.120,121 There is evidence value and it has been described by Mattson and
that it could be inhibited by the presence of organic Fredriksson.127 The crusts covering these pits are
species in the water.122 less voluminous than Type I pits, the cavities are
This evidence has been corroborated in the United branching and they may be almost completely filled
Kingdom by Campbell, who found failures due to this with black cuprous oxide. The occurrence of Type II
effect were confined to certain districts that is, supply pitting is associated with waters with pH  7 and low
waters. He showed that for many supply waters this carbonate contents. A successful remedy has been to
increase pH, introduce carbonate dosing to give a
minimum of 70 mg HCO
3 per liter, or reduce the
water temperature to less than 60  C.
3.07.3.4.1.3 Type III pitting
This type of pitting occurs in cold soft waters with a
pH above 8.0 and it is geographically localized, being
mainly confined to Sweden. It is generalized form of
pitting where the pits are sparse128,129. Mattson128
describes the phenomenon, noting its morphology
and means of avoidance through a method involving
bicarbonate dosing of the drinking water.

3.07.3.4.1.4 Electrochemistry of pitting

Drogowska et al.130 have used solutions designed to
mimic natural waters containing bicarbonate and
Figure 3 Photograph showing carbon film pitting on a chloride ions to study the anodic oxidation of copper
copper tube. and onset of pitting corrosion. They have found that,
1956 Non-Ferrous Metals and Alloys

as the anodic polarization of copper increases in this This will normally take place in the first few months
environment, a porous layer of Cu2O initially forms after installation. An example of this is shown in Fig-
on the metal surface. This is found to convert to basic ure 4. Over longer periods when the active elements
CuCO3 at more positive anodic potentials or in higher of the flux are exhausted, the presence of residue can
concentrations of HCO
3 ions. A passivity breakdown lead to deposit attack. In both of these cases, pitting
potential is recorded at which pitting initiates, and this corrosion and failure of the tube can result. Good
becomes more positive when HCO
3 ions are present. installation practice which ensures complete removel
The presence of Cl
ions shifts the pitting potential to of any flux residue by washing (as given by BS
lower values, but the HCO
3 ions are found to act to 6700:1997) will prevent this type of corrosion. Capil-
prevent this effect. Sulfate ions are found to have a very lary joints formed using copper/phosphorus, copper/
similar effect to chloride ions in lowering the break- silver/phosphorus, or silver brazing alloys do not need
down potential131 and pitting is found to be avoided flux and therefore cannot suffer this type of attack.
if the pH  7.4 and the [HCO
3 ]/[SO4 ] ratio is 1.
2

The effect of increasing the solution temperature 3.07.3.4.3 Microbiologically influenced

to 60  C is found to give improvement to the passivity corrosion
of the oxide film.132 Two new international standards Microbiologically influenced corrosion (MIC),
have been produced which give guidance on cor- describes a form of pitting considered to be due to
rosion prevention in water distribution and storage the action of microbes. This form of corrosion of metals
systems.133 has been known for many years, for instance in the oil
industry, and an early description of its occurrence
3.07.3.4.2 Chemical attack with copper alloys was given by Rogers in 1948.134 In
Joining copper should be accomplished according to some instances, MIC has been associated with soft
recommended practice to avoid corrosion issues. water which is high in organic content which has
Copper pipework installations are joined using capil- been allowed to maintain temperatures in the region
lary attraction of solder or braze material or by of 20–30  C under low velocity conditions. In such
mechanical means. circumstances, the resulting warm high concentration
In the case of capillary joints, fittings, or in some of organic material at the bottom of horizontal tubes
cases specifically formed tube ends, are used to form provides ideal conditions for MIC to take place.135
an annular capillary gap into which molten solder or Other circumstances with a different water quality
braze is run. Fluxes containing chlorides have to be have been described by Wagner et al.136 However, the
used when soldering. The chlorides act to remove exact MIC mechanism has not been elaborated. The
surface oxide and reduce the surface tension, allow- general view is that a region of low pH is created under
ing the solder to be drawn into the capillary gap. a biofilm containing polysaccharides and that the
Excessive use of flux can lead to its retention in organic materials present provide transport for the
the pipework and attack by the chloride ions present. metal ions to the liquid phase.137

Typical protective
corrosion layer

Soldering Flux run-off and leak

Figure 4 Photograph showing flux attack on a soldered copper tube.

 Corrosion of Copper and its Alloys 1957

Figure 5 Optical micrograph showing an example of the

Figure 6 Photograph showing longitudinal stress
typical pit morphology found in MIC.
corrosion cracking of a 15 mm diameter copper tube (EN
1057, R250, half-hard condition).

MIC of copper water pipes in institutional build-

ings has been reported in several countries. The impingement attack occurs. A few very hard waters
results of research, leading to remedial measures, can also give rise to copper dissolution. Research has
have been summarized by Geesey.138 indicated that the difference between a scale forming
An example of this type of corrosion associated water (with a resulting low copper dissolution rate)
with soft high organic content water is shown in and a ‘dissolving’ hard water appears to be organic
Figure 5. Avoidance entails operating the system at content.142
correct temperatures and flow rates as well as provid- High levels of copper complexed with organic
ing water with a low organic burden and with the material gives the water a distinctive blue color, and
implementation of appropriate disinfection measures. is hence given the term ‘blue water corrosion.’ It
tends to be confined to soft, unstable water types
3.07.3.4.4 Stress corrosion cracking and, to date, appears to be confined to Australia and
Stress corrosion cracking (SCC) may occur with brass New Zealand. This form of dissolution has been
fittings (see Section 3.07.3.6.1) due to traces of found to be due to microorganisms143 and restoring
ammonia in the environment or arising from nitrates the disinfection agent (e.g., free chlorine) to its
in the water. In certain rare instances, copper tubes desired level will stop the effect and prevent the
are known to suffer SCC, an example of which is occurrence of further episodes.
shown in Figure 6. In the great majority of cases of A review of the current state of knowledge
stress corrosion encountered, traces of ammonia have on dissolution in drinking water has been prepared
been found in the cracks. by Merkel and Pehkonen.144 In considering copper
dissolution, this paper subdivides general copper
3.07.3.4.5 Dissolution corrosion into the subprocesses (oxidation, scale
The corrosion of copper in contact with drinking formation, and scale dissolution) enabling a better
water soon reduces to a very low rate due to the understanding of the influence of water quality para-
formation of stable scale. However, some waters meters and operating conditions on copper release.
continuously dissolve appreciable amounts of cop- This work also considers that research needs to
per.139–141 Factors which favor this action are waters be carried out to distinguish between organic com-
with low pH and low total dissolved solids. There- ponents which promote or reduce the dissolution
fore, most dissolution is found in hot, soft, acid waters. process.
Desalination plants will produce such an aggressive Once copper has been dissolved, it may then lead
water and unless treated to increase its mineral con- to problems downstream. For instance, the dissolved
tent this water should not be used with copper. This copper can (1) plate out and cause galvanic corrosion
type of corrosion is general and the resulting pipe on other products such as zinc-coated steel,145 light
wall thinning is so slight that the useful life of the alloys,146 or bare steel and (2) cause blue–green stain-
pipe or component is virtually unaffected unless ing in baths, sinks, and sometimes clothes or hair due
1958 Non-Ferrous Metals and Alloys

to the combination of copper with stearates in soaps contamination causes serious corrosion if polluted
and shampoos. and aerated conditions alternate, or if oxygen and
The World Health Organization (WHO) Guide- sulfide are simultaneously present.
lines for Drinking Water Quality 1993147 notes that Corrosion of condenser tubes was a problem of
copper is an essential element necessary for human great magnitude during the first quarter of the twen-
health and that in most parts of the world deficiency tieth century. In those times, 70–30 brass condenser
was a problem. However, it was decided that setting tubes failed by dezincification and Admiralty brass
an upper limit for the allowable concentration was (70Cu–29Zn–1Sn) was brought into use. This proved
necessary. Following this guideline, many countries little better, but some time later the addition of arsenic
have regulated the maximum weekly average of was found to inhibit dezincification. Failures of Admi-
drinking water to 2 mg Cu per liter. Araya et al.148 ralty brass by impingement attack became a serious
showed that the likely taste level for copper in drink- problem, particularly as cooling water speeds increased
ing water was 4 mg l
1 or above for 95% of the with the development of the steam turbine. The intro-
population. duction of alloys resistant to impingement attack was a
In deaerated conditions, for instance, in most great step forward and immediately reduced the inci-
central heating systems, little attack on copper dences of failure. A history of condenser tubes up to
occurs.149–151 Further reference to the subject of cop- 1950 has been published by Gilbert.158
per in water can be found in an extensive review by The alloys most commonly employed today are
Grunau.152 cupronickels,159 containing appropriate iron and
manganese levels and aluminum brass (76Cu–22Zn–
2Al–0.04As). Three cupronickel alloys are in wide-
3.07.3.5 Corrosion in Seawater
spread use and these are: (1) 30Ni–0.7Fe–0.7Mn, (2)
Copper alloys have had an extensive history of use in 30Ni–2Fe–2Mn, and (3) 10Ni–1.5Fe–1 Mn. These
a wide range of marine applications9,153 due to their materials are extensively and successfully applied in
advantageous properties with respect to corrosion ships, power stations, oil refineries, desalination
and biofouling resistance, conductivity, and ease of plants, etc., in condensers and heat exchangers, with
fabrication. limitations on water flow velocities, sometimes with
Exposure tests of various copper alloys have been much entrained air present. At the highest water flow
carried out in natural seawater by the UK Ministry of velocities, there is a rather greater factor of safety
Defence laboratories.154 Weight loss measurements with 70–30 cupronickel. The 30Ni–0.7Fe–0.7Mn var-
were used to measure general corrosion rates, crevice iant is usually to be preferred under most polluted
corrosion rates, and erosion/corrosion flow velocity water conditions.
limits. The results are shown in Table 7, although A number of studies have been carried out on the
some anomalies have been reported for the dta as reasons for the high seawater corrosion resistance of
presented75. It was found that the brasses exhibited cupronickels. In 70–30, a nickel-rich zone is formed
the highest corrosion rates and the alloys most resis- in the oxide layer at the metal surface.160 This acts to
tant to corrosion and erosion/corrosion were the anodically protect the matrix from further corrosion.
cupronickels. If the film develops defects, which may be caused by
Regarding practical applications of copper alloys prior deformation of the metal,161 then corrosion
in seawater, a major example is their use for conden- initially accelerates in those areas, but quickly
sers and heat exchangers, which has been long estab- diminishes, resulting in a smooth overall surface.
lished. Recent reviews have considered potential The occasional failures which still occur in con-
corrosion in this application, the likely causes and denser tubes are usually due to one (or sometimes
remediation procedures.76,155–157 Specific aspects several) of the following factors:
covered include the effects of surface films, the com-
missioning process, stagnant conditions, flow veloc- 1. Localized attack or pitting in badly contaminated
ity, ferrous sulfate treatment, and cleaning waters.
techniques. The latter may lead to greater corrosion, 2. Pitting under decaying barnacles, shell fish, or
though ferrous sulfate treatment can offset the effect. other deposits.
Chlorination can cause increased attack in some cir- 3. Impingement attack due to high local water velo-
cumstances, aluminum brass being more susceptible cities, e.g., at partial obstructions in a tube such as
to attack than cupronickels. The presence of sulfide barnacles or Hydra.
 Corrosion of Copper and its Alloys 1959

4. Erosion due to sand or other abrasive particles their use, a period of 3 weeks or more should be
suspended in the water. imposed during which natural seawater is allowed to
5. Use of tubes of the wrong alloy, or of incorrect flow through the system to restore passivity.
composition or which contain manufacturing Condenser tube-plates of naval brass usually
defects. undergo some dezincification in seawater service,
6. Poor welding techniques causing welds to pro- but this is normally not serious in view of the thick-
trude into the flow. ness of the metal involved. Use has been made of
tube-plates of more resistant materials such as alumi-
The material most commonly used when suspended num bronze, or cupronickel. Plates that are too large
abrasive matter is a problem is the 30% Ni alloy to be rolled in one piece can be fabricated by welding
containing 2% each of Fe and Mn.156,157 together two or more items. In some special applica-
A difficult condenser-tube corrosion problem tions, the tubes are fusion welded or explosively
arises from the use of polluted cooling waters from welded to the tube plates. Fusion welding operations
harbors and estuaries, which may be severely con- are rather more difficult with brasses than with other
taminated, particularly when warmer climates are copper alloys due to the evolution of zinc fume
involved.162 Many condenser-tube materials are lia- during the process.
ble to suffer corrosion in these circumstances, and the Condenser water-boxes were at one time made of
choice of materials is made difficult by the fact that unprotected (or poorly protected) cast iron and these
different orders of merit apply at different locations afforded a measure of cathodic protection to the tube
and even at the same location at different times. The plates and tube ends. This beneficial effect has been
state of the water when the tubes are commissioned lost with the general adoption of water-boxes which
and first enter service, which influences the type of are completely coated with rubber or some other
surface film formed, may well determine whether or impervious layer, or which are made from resistant
not a satisfactory service life will be obtained.159,163 materials such as gunmetal, aluminum–bronze, or
Full salinity seawater, free from sulfides, is reported cupronickel. Steel water-boxes which are clad with
to be the most effective passivating medium162 cupronickel are also used. To prevent attack on tube-
although the 14–60 days which this takes to complete plates and tube-ends in these circumstances, either a
may put it at a lower ranking than other methods, suitable applied-current cathodic protection system
particularly those involving dosing with ferrous can be applied or sacrificial soft-iron or mild-steel
sulfate76. anodes can be installed, the required protection volt-
In power plants, the condenser tubes must be able age being fairly low (50 mV minimum).169 Ferrous
to withstand corrosive cooling waters and complex wastage plates have the additional advantage that the
boiler water treatments. Also, the use of recirculating iron corrosion products introduced into the cooling
water can cause dissolved salts to concentrate between water assist in the development of good protective
twice and eight times the initial concentration, making films throughout the length of the tubes. This is
the water significantly more aggressive.164 Corrosion of particularly important in the case of aluminum–
power-station condenser tubes by polluted waters brass tubes; indeed, with such tubes it may be desir-
was at one time particularly troublesome in Japan. able, as an additional preventative measure, to add a
Improved results have been reported using tin brasses suitable soluble iron salt (such as ferrous sulfate)
or special tin bronzes.165 Elsewhere, pretreatments regularly to the cooling water.
have been investigated with mixed success76,166 and As it has become increasingly necessary to supple-
sodium dimethyldithiocarbamate is reported to give ment natural sources of freshwater in various parts of
protective films which will withstand the action of the world, processes for producing freshwater from
polluted waters167 and has had some naval use.76 seawater have been intensively studied. Distillation is
Methods of maintaining tube cleanliness include one method widely used and, during recent years,
chlorination and mechanical methods such as water large numbers of multistage flash-distillation plants
lancing and the use of the Taprogge system of circu- have been installed in various countries particularly
lating sponge-rubber balls.157 Hot acid is now not in the Middle East. Many of the larger flash-distillation
environmentally acceptable and the use of commer- units are capable of producing several millions of
cial descaling agents invariably results in the near gallons of freshwater per day. In these plants, seawater
complete loss of the passive surface layers on the passes through horizontally disposed tubes and
material.168 Thus, it is recommended that, after steam, which is ‘flashed’ from the brine, condenses
1960 Non-Ferrous Metals and Alloys

on the outside. In some parts of the plant, the condi- shown that the normal additions of arsenic to inhibit
tions are similar to those in steam condensers, but in dezincification (0.04%) have no significant adverse
other parts the seawater has been treated to remove effect. Other possible consequences of exposing cop-
dissolved gases and is at much higher temperatures. per alloys to seawater which have been investigated
Copper alloy tubes are used in large numbers for the included dealloying of aluminum bronzes109 and the
heat exchange units in this type of desalination effects at bimetallic contacts.
plant,170,171 these being mainly aluminum–brass and Major efforts have been made to understand the
the various cupronickel alloys. nature of films formed on copper alloys in natural
For cooling-water trunking and saltwater services seawater. These films have quite different character-
in the engine room and elsewhere, including fire istics to those formed in sodium chloride solution, the
mains, plumbing, and air-conditioning systems in differences being associated with the presence of
ships, more resistant alloys are taking the place of organic material in the natural environment. However,
copper or galvanized steel. The latter were formerly the structure of the films is affected by variables such
extensively employed, but they do not have adequate as water velocity, temperature, and oxygen content.
resistance to attack by seawater. Cu–10Ni–1.5Fe alloy Protective films often have a multilayered structure,157
has been widely utilized and normally gives excellent with an outer layer rich in iron providing impinge-
service. In some special naval applications, pipelines ment resistance and an inner layer giving chemical/
of 70–30 cupronickel are used and it has been found electrochemical protection. With aluminum brass,
that adequate attention must be given to correct a colloidal mixed hydroxide inner layer provides a
fabrication and installation techniques. Carbonaceous buffering action, with tin-containing brass there
residues from fillers used in bending operations must is a tin-rich layer near the copper surface173 and,
be avoided or pitting corrosion may occur in service. with cupronickel, there is a chloride-rich layer which
Jointing materials of low corrosion resistance should strongly inhibits the cathodic reaction. A study on Cu–
not be used, silver brazing or appropriate welding Si alloys in seawater has found that the formation of
methods being the correct techniques. Residual stres- copper silicide at the alloy surface acts to prevent
ses, if present, can cause stress-corrosion failures of corrosion.174
aluminum–brass pipelines in service.
Copper alloys in wrought or cast form are employed
3.07.3.6 Effect of Exposure to
for other purposes in ships and marine installations,
Contaminated Environments
such as for propellers, bearings, valves, and pumps. For
instance, aluminum–brass is used for heating coils in As with many metallic materials, failure of copper
tankers carrying crude oil or petroleum products. alloys may occur by cracking due to the combined
However, some corrosion problems encountered in influence of tensile stress and exposure to a debilitat-
this and other applications on board ship have been ing environment due to the presence of a contami-
described by Gilbert and Jenner.172 nant. Failures of brass components due to this form of
Cupronickels have been shown to possess ex- stress corrosion cracking have been known for many
tremely low long-term corrosion rates in quiet or years175 and has been termed season cracking. In this
slowly-moving seawater. The 90–10 alloy is of partic- case, the stresses in the material are produced
ular interest28,163: this alloy is now well established in components during their manufacture and the
for use for pipelines on ships and it has become contaminant is ammonia vapor produced by the nat-
widely used for piping systems on floating produc- ural decay of organic matter.
tion, storage and offloading vessels (FPSO’s), and Only certain specific environments appear to pro-
offshore platforms. In addition to its good corrosion duce stress corrosion of copper alloys, most notably
resistance, 90–10 cupronickel has a high resistance to ammonia,176–178 ammonium compounds, or amines.
marine macrofouling providing that it is not cathodi- Interestingly, pure copper does not suffer from
cally protected. This has led to applications such as ammonia-induced stress corrosion but will display
the construction or sheathing of ships’ hulls, fish the phenomenon in the presence of nitrites.179 Stress
cages for aquaculture and cladding of steel offshore corrosion can also occur with moist sulfur dioxide,
structures in the tidal/splash zones.9 sulfites, and some organic acids.180 Mercury or
Investigations into the effects of arsenic and phos- solutions of mercury salts (which cause deposition
phorus in single phase brasses on their susceptibility of mercury), or other molten metals will also
to intergranular attack and SCC in seawater have cause cracking, but the mechanism is undoubtedly
 Corrosion of Copper and its Alloys 1961

different.181 Cracks produced by mercury are always guarantee freedom from cracking in environments
intergranular, but ammonia, according to the exact containing ammonia. More searching tests involving
conditions, may produce cracks which are fully trans- exposure to ammonia have therefore been devised,
granular, fully intergranular, or a mixture of both. As such as ISO 6957:1988. The standardization of stress-
an illustration of this, Edmunds182 found that mer- corrosion cracking tests and their correlation with
cury would not produce cracking in a stressed single service experience have been the subject of several
crystal of brass, whereas ammonia could do so. papers.196–200 A European standard for the assessment
In certain circumstances, corrosion of copper of susceptibility to SCC was published in 2006: EN
alloys can occur through seemingly random 14977, Copper and copper alloys – detection of tensile
interconnected microtunnels which spread out into stress – 5% ammonia test. Many authors201–205 have
the metal from what appears to be only a discolor- described practical cases of stress-corrosion crack-
ation of the surface film. As a result of this phenom- ing usually involving tensile stresses applied in ser-
enon, through-thickness perforation of tube can vice. Two possible preventive measures are the use of
result in weeks or months. This type of corrosion coatings206–208 or inhibitors.209
has been termed formicary corrosion due to its mor- The behavior of a wide range of a, a–b, and b
phological similarity to an ants nest. Elliott183 has brasses in various corrosive environments was studied
produced a summary of knowledge of formicary cor- by Voce and Bailey and their results have been sum-
rosion up to 1999. The cause has been ascribed to marized by Whitaker.210 Penetration by mercury and
contamination of the outside of the tube by carbox- by molten solder was found to be intergranular in
ylic acids. all three types of brass. In moist ammoniacal atmo-
spheres, the penetration of unstressed brasses of all
3.07.3.6.1 Stress corrosion of brasses types was intergranular. Internal applied stresses
Brasses containing only a few percent of zinc may accelerated the intergranular penetration of a brasses
crack under load if the stresses are high and the and initiated some transgranular cracking. It also
environment is sufficiently corrosive and most types caused severe transgranular cracking of b alloys
of brass appear to be susceptible to the occurrence of and transgranular cracking across the b regions
this phenomenon of stress corrosion. An investigation in the two-phase brasses. Immersion in ammonia
of the effect of additions to 70–30 brass has been solution, however, caused intergranular cracking of
carried out by Wilson et al.,184 who found that an stressed b brasses. b brasses containing 3% or more
addition of 1% Si was markedly beneficial. Other aluminum failed with an intergranular fracture when
additions were beneficial under some circumstances stressed at 0.1% proof stress in air. The behavior
but none of the 36 additions tested accelerated stress- of alloys of this type was subsequently studied by
corrosion cracking. Further results have been given Perryman211 and Bailey212 who showed that cracking
in later papers.185,186 in air occurs only when moisture is present. It has
In general, the susceptibility to stress corrosion in been confirmed that b brasses are prone to crack in
brasses appears to rise with an increase of zinc con- service.213
tent, but in some circumstances alloys containing High-strength a–b brasses containing up to 5%
64–65% Cu were found to be rather more affected Al (with small amounts of Fe, Mn, Sn, etc.) used for
than those containing 60% Cu.187 propellers, parts of pumps, nuts and bolts, and similar
Many workers188–193 have investigated the resid- applications usually give good service but occasion-
ual stresses introduced by different working pro- ally suffer intergranular failure, for instance in con-
cesses in brasses of various compositions and the tact with seawater. Examination of such failures
annealing treatments necessary to remove these usually reveals thin dezincified layers along the
stresses or reduce them to a safe level. A ‘stress-relief cracks, but it is often difficult to decide whether the
anneal’ at 300  C will usually lower internal stres- crack or the dezincification occurred first.
ses to comparatively small values without much The theoretical aspects of stress-corrosion crack-
effect on hardness of the material. ing have attracted much attention in recent years.
Specifications for brass products customarily Among the copper alloys, the behavior of brasses in
include the provision for carrying out a mercurous ammoniacal environments has been most studied.
nitrate test194,195 (EN ISO 196:1995) to ensure While cracking has been shown to be possible in
that unduly high residual tensile stresses are not contact with some other corrosive agents, ammonia
present, but a satisfactory result in this test does not has the most powerful effect. Evans214 suggests that
1962 Non-Ferrous Metals and Alloys

this is because ammonia is a feeble corrodent which of zinc content, but with most other elements there
produces little attack except at regions such as grain was a minimum in the curve of concentration of alloy-
boundaries or other lattice imperfections. Also, it ing elements against time to failure. In tests carried out
prevents accumulation of copper ions in the crevices under a static load of 70 MN m
2, these minima were
formed owing to the formation of stable complexes found to occur at concentration levels of 0.2% P,
such as Cu[(NH3)4]2+. The mode of cracking (inter- 0.2% As, 1% Si, 5% Ni, and 1% Al. In most cases, the
granular or transgranular) can be affected by changes cracking was observed to be intergranular.
in composition of the brass or by changes in the A series of slow strain rate tests have been carried
nature of the environment.215 Mattsson216 found out on high strength Cu–Ni–Al alloys in environ-
that, on immersion in ammoniacal solutions of differ- ments which could be encountered by the offshore oil
ent pH values, stressed brasses cracked most rapidly and gas industry276 and these have found that the
at pH 7.1–7.3 and that in this range black surface application of a cathodic potential (as applied in
films formed on the metal. The role of tarnish films cathodic protection) gives protection against stress
has been further studied subsequently.217–219 Many corrosion. However, molybdenum disulfide greases
authors have studied electrochemical220–235 or met- mixed with seawater and greases containing bentone
allurgical236–241 aspects of the stress corrosion of were found to promote stress corrosion as did the
copper alloys and discussed theories of the mecha- more well known debilitating species such as amines.
nism. Papers on the subject have been included in Work on relating the microstructural aspects of these
several symposia or conferences on stress corrosion alloys to their possible susceptibility to stress corro-
of metals.242–244 The stress cracking of brasses has sion has identified277 that the production process
been reviewed by Bailey245 and other workers246–254 should be undertaken in such a way that the presence
and reviews of stress corrosion as a general subject of iron-rich phases on the grain boundaries is
have also been published.255–257 restricted, the material has a fine grain size and that
it is supplied in an under-aged condition.
3.07.3.6.2 Stress corrosion of other copper Cupronickels (90–10 and 70–30) have generally
alloys been considered immune to sulfide stress corrosion
Evidence indicates that pure copper is not likely in most seawater environments.9 However, there have
to be susceptible to stress corrosion258–260 but been recent trials278 in seawater containing severe
instances of the failure of copper are known, when sulfide levels of 100–1000 ppm which indicate a
it contains 0.4% As261 or 0.02% P.258 SCC has cracking possibility for the 90–10 alloy.
also been found to occur in copper–beryllium,262 A related debilitating effect to stress corrosion
copper–manganese,263–265 aluminum–bronzes,266,267 cracking is hydrogen embrittlement, and it is inter-
tin–bronzes, silicon–bronzes, nickel silvers,268 and esting to note that copper alloys have not been
cupronickels.268,269 Most of these alloys are much reported to suffer from this phenomenon. In particu-
less susceptible to cracking than brasses,270 although lar, testing has demonstrated that high strength Cu–
under some conditions aluminum–bronzes can be Ni–Al and Cu–Ni–Sn alloys do not embrittle under
particularly prone to cracking.271 In ammoniacal hydrogen charging conditions277 whereas nickel
environments, the cracking tends to be transgranular, alloys containing copper and aluminum (Ni–Cu–Al)
and in steam atmospheres, intergranular cracking is lose ductility under the same conditions. Detailed
favored.272 Additions of 0.35% Sn or Ag are claimed electrochemical work carried out by Pound279 allowed
to be effective in preventing intergranular crack- him to suggest that this is because the internal hydro-
ing.273,274 Aluminum–bronzes containing 2% Ni gen becomes associated with both reversible and irre-
and 0.5–0.75% Si are claimed to have good resistance versible trap sites. He postulates that the trap sites in a
to stress corrosion,273,275 although there is evidence Cu–Ni–Al alloy are measurably more reversible than
that silicon bronzes can show accelerated intergranu- those in Ni–Cu–Al, preventing the former from being
lar fracture in the presence of moist air. susceptible to hydrogen embrittlement.
Thompson and Tracy258 carried out tests in a
moist ammoniacal atmosphere on stressed binary
3.07.3.7 Corrosion in Industrial Chemicals
copper alloys containing zinc, phosphorus, arsenic,
silicon, nickel, or aluminum. All these elements gave A number of publications are available which give
alloys susceptibility to stress corrosion. In the case of detailed information on the action of a wide range of
zinc, the failure time decreased steadily with increase chemicals on copper and copper alloys.280–285
 Corrosion of Copper and its Alloys 1963

When contemplating the use of copper-based of flow.296 Tin–bronzes, aluminum–bronzes,297–299 sili-

materials for industrial purposes it is necessary to con–bronzes, and cupronickels are among the copper
bear in mind that, even though a satisfactory life of alloys most resistant to acids. For instance, aluminum
the component may be obtained, possible difficulties bronze will withstand 50% sulfuric acid at 120  C and
may arise from the following other causes: 60% sulfuric acid at 30  C. Silicon bronze is resistant
to hydrochloric acid over the range 10% HCl at
1. Copper compounds can be tolerated only in small
70  C/20% HCl at 50  C/35% HCl at 15  C. Brasses
amounts in potable waters or food substances. The
should not normally be used in acids. All copper-based
WHO current safe concentration limit for copper
materials are attacked rapidly by oxidizing acids such
in drinking water of 2.0 mg l
1.
as nitric acid, strong sulfuric acid, or chromic acid
2. Copper compounds are highly colored, and a very
(including dichromates) and also by hydrocyanic acid.
small amount of corrosion may lead to staining
The maximum temperature of operation of copper in
and discoloration of products.
dry HCl is 93  C and in dry chlorine it is 200  C.
3. Stimulation of the corrosion of vital parts made of
The dissolution of copper and brasses in acid
more anodic metals may occur if they are
solutions has been studied by several authors.300–305
connected to copper.
In sulfuric acid, pitting attack has been found to occur
4. Very small amounts of copper taken into solution
in 95% sulfuric acid at 50  C, in 80% sulfuric acid at
may cause considerable corrosion of more anodic
70  C, and in 60% sulfuric acid at 100  C. Various
metals elsewhere in the system, particularly
substances have been found to have an inhibiting
zinc,145 aluminum,146 and sometimes steel.286
effect on the rate of attack of copper or brasses in
Small particles of copper deposited from solution
nitric acid306–310 and in hydrochloric acid.311
set up local cells which can cause rapid pitting.
Despite these qualifications, copper and its alloys 3.07.3.7.2 Neutral and alkaline solutions
are used extensively and successfully in many types Copper-based materials are resistant to alkaline solu-
of chemical production equipment. Uses include tions over a wide range of conditions,312 but may be
condensers and evaporators, pipelines, pumps, appreciably attacked by strong solutions, particularly
fans, vacuum pans, and fractionating columns. Tin– if hot. Cupronickel alloys usually give the best results
bronzes, aluminum–bronzes, silicon–bronzes, and in alkaline solutions. Copper and its alloys should
cupronickels are used in some circumstances because be avoided if ammonia, ammonium compounds, or
they present better corrosion resistance than copper organic amines are present313–317 owing to the danger
or brasses. of both general corrosion and stress corrosion.
Copper is satisfactory for handling solutions of
3.07.3.7.1 Acid solutions most neutral salts280,318 unless aeration and turbu-
Copper does not normally displace hydrogen, even lence are excessive. All exception is provided by
from acid solutions, and it is therefore virtually un- those salts that form complexes with copper, such as
attacked in nonoxidizing conditions. For strongly cyanides, and solutions containing oxidizing agents,
reducing conditions in the temperature range 300– such as ferric or stannic compounds.
400  C, corrosion resistance is comparable, if not
better, than stainless steel. However, when copper 3.07.3.7.3 Hydrogen sulfide pollution
alloys come into contact with most solutions, which Polluted and stagnant waters can be a source of
invariably contain dissolved air, cathodic depolariza- corrosion to copper alloys because of the metal reac-
tion can occur which increases the chances that cor- tion with hydrogen sulfide to form sulfide surface
rosion will take place.287 Therefore, it is difficult to lay films. Higher corrosion rates and pitting corrosion
down any general recommendations for the use of can result because the films do not provide the same
copper in acid solutions, since the rate of attack signifi- protection as those normally formed. Sources of
cantly depends on the particular circumstances. hydrogen sulfide include industrial waste, decomposi-
Under fairly mild conditions copper or copper alloys tion of organic matter, and sulfate reducing bacteria.
are successfully used for handling solutions of hydro- When there is little or no oxygen present in the
fluoric,280,288,289 hydrochloric,280,290 sulfuric,291 phos- system, then the corrosion rate of copper alloys with
phoric,280,292 acetic, and other fatty acids.280,293 Rates a sulfide film is only slightly higher than in aerated
of corrosion, in general, increase with concentration of seawater.319 However, when aerated seawater mixes
acid, temperature, amount of aeration,294,295 and speed with sulfide-containing seawater, higher rates of
1964 Non-Ferrous Metals and Alloys

corrosion can occur. Such corrosion is also velocity spot corrosion can be found in heat exchangers from
sensitive and is found to be more pronounced in 130  C down to 80  C. This type of attack is caused
regions of highest flow velocity. by thermogalvanic effects under slow flow or stag-
A sulfide film can gradually be replaced by an nant conditions. Cupronickel (70–30) is the most
oxide film in seawater during subsequent exposure susceptible alloy for hot spot corrosion and alumi-
to aerated conditions,9,162 although this may take num brass is the most resistant. Again, ferrous sulfate
several days and high corrosion rates can be expected dosing, or higher flow rates, can provide improved
in the interim. However, if an established cuprous resistance.
oxide film is already present, then periodic exposure A microstructural study of the behavior of high
to polluted water can be tolerated without damage to strength Cu–Ni–Al alloy toward aqueous H2S has
the film. Therefore, exposure to sulfides should be been carried out using STEM and SEM surface
restricted wherever possible and this should be par- analysis.320 The morphology of the surface is shown
ticularly so during commissioning and during the in Figure 7 together with a schematic diagram
first few months of exposure to seawater, during derived from microanalysis explaining the chemical
which time the oxide film is maturing. Typical guide- composition of the various corrosion product layers
lines for commissioning or shut down/standby of formed. It was concluded that the large copper sul-
copper alloy piping systems are given in Table 8. fide crystals were deposited on the surface following
The addition of ferrous ions to seawater systems, preferential corrosion of copper from the alloy sur-
usually as a result of dosing with ferrous sulfate or by face. The general corrosion rate was about three
the use of a stimulated iron anode, has been found to times lower than that of 70–30 cupronickel as a result
improve the corrosion resistance of aluminum brass of the formation of an aluminum-rich oxide layer
and cupronickels when exposure to polluted condi- directly at the solid/solution interface.
tions are anticipated.76 Other pretreatments have
been investigated with variable success.76,166 3.07.3.7.4 Other chemicals
The common cast alloys used for seawater systems Copper and copper alloys are unsuitable in hydrogen
are gunmetals, high tin bronzes, and nickel aluminum peroxide279,321 or molten sulfur.279,322 Halogens
bronze. In clean water, nickel aluminum bronze is the have little action on copper at room temperature
favored alloy for pumps and valves319 but 10% tin when dry, but are corrosive when wet. Hypochlorite
bronzes can be better in mildly polluted conditions, solutions are corrosive.323 Most organic compounds
particularly for erosion resistance. are without appreciable action,279 although contact
Francis has reported319 that the presence of sul- with moist acetylene should be avoided, as explosive
fides can reduce the temperature above which hot compounds are formed. Moisture also accelerates

Table 8 Guidelines for shutdown and standby conditions of a copper alloy piping system in order to avoid possible
problems caused by the presence of sulfides

Conditions in the system

Duration Clean seawater or freshwater without deposits Polluted seawater or freshwater where deposits
are present

4–6 days Keep the system filled Commissioned system:

Avoid high flow rates
If possible, drain the system and fill with clean
seawater or freshwater
New system:
Clean the system and fill with clean seawater
or freshwater.
>4–6 days Keep the system filled and replace the water by Possibility I:
oxygenated water every 2–3 days Clean the system and fill with clean seawater
or freshwater
Replace the water by oxygenated clean
water every 2–3 days.
Possibility II:
Clean the system and keep it dry.
 Corrosion of Copper and its Alloys 1965

Thick sulphide rich layer Thin sublayer

Corrosion
product

Metal

(a)

Thick scale containing sulphide

partially converted sulphuric and oxide Oxide rich scale
Partially converted subscale

Corrosion product

Metal

(b)
Figure 7 Scanning electron image and schematic diagram of Cu–Ni–Al surface after exposure to saturated aqueous
H2S at 25  C.

attack by halogenated organic compounds, particularly At 180–290  C, it has been determined334 that the
carbon tetrachloride and trichloroethylene, which parabolic law first applies but, subsequently, this
hydrolyze to give traces of hydrochloric acid. Cupro- changes to a logarithmic relationship of the type
nickels show most resistance to these chemicals. shown in eqn [7]:
Copper alloys are widely used for handling hydro-
Y ¼ K logBðt þ 1=BÞ ½7
carbon oils, although, if sulfur compounds are pres-
ent, attack can be serious. The effects of synthetic B being a constant. However, other workers have
detergents on copper have been investigated324,325 reported a cubic relationship under some conditions.
and several authors279,326–328 have discussed various Evans335,336 has shown how the effect of internal
aspects of the behavior of copper and its alloys in the stresses in growing films may have various effects
food-processing industry, where direct contact with which can lead to any one of the three growth laws
copper alloys can result in the alteration of taste referred to above.
or color. At medium and high temperatures337–345 copper
ultimately follows the parabolic law.346 It has
been shown using radioactive tracers347,348 that the
3.07.3.8 High Temperature Oxidation and
diffusion of copper ions in cuprous oxide is the rate-
Scaling
determining step at 800–1000  C, and there is con-
Several authors have reviewed the literature on the siderable evidence in favor of the view that metal ions
oxidation and scaling of metals, including copper.329–332 move outwards through the film by means of vacant
sites in the oxide lattice.133
3.07.3.8.1 High temperature oxidation of When oxidation is a diffusion-controlled process,
copper the oxidation rate should be related to the tempera-
The volume ratio for cuprous oxide on copper is 1.7, ture by the Arrhenius relationship, eqn [8]:
so that an initially protective film is to be expected.
K ¼ A expð
Q =RTÞ ½8
Such a film must grow by a diffusion process and
should obey a parabolic law. This has been found to where K is the rate constant, A a constant, R the
apply for copper in many conditions, but other rela- gas constant, T the absolute temperature, and Q
tionships have been noted. For instance, in the very the activation energy. Values which have been
early stages of oxidation, a linear growth law is found obtained for A and Q are summarized by Tylecote,349
(e.g., at 1000  C).333 Pilling and Bedworth,350 Feitknecht,351 and others
1966 Non-Ferrous Metals and Alloys

and give values of Q of 0.17 MJ for temperatures and this theory is supported by the fact that the
of 700–1000  C, while at lower temperatures (up alloying elements giving maximum oxidation resis-
to 500  C) Vernon352 and others have obtained tance to copper, that is, beryllium, aluminum, and
values of about 85 kJ. These values are in agreement magnesium, form oxides having very low conductiv-
with calculations by Valensi,353 based on the assump- ities, as shown by Price and Thomas.372 Wagner cal-
tion that, at high temperatures, the oxidation proceeds culated that when sufficient aluminum was present in
by the reaction of oxygen with metallic copper to copper to cause the formation of an alumina film, the
produce cuprous oxide while at lower temperatures oxidation rate should be decreased by a factor of
the rate is determined by the reaction between oxygen more than 80 000. Experiment showed the factor to
and cuprous oxide to form cupric oxide. be only 36, but when Price and Thomas carried out
At low temperatures (e.g., 300  C) the film consists initial oxidation under only slightly oxidizing condi-
almost entirely of CuO. As the temperature increases, tions, producing only a film of alumina, the oxidation
the film consists of a layer of Cu2O beneath a layer rate on subsequent exposure to full oxidizing conditions
of CuO, the proportion of Cu2O increasing until, was decreased by a factor of 240 000. Hallowes and
at high temperature, the film is almost entirely Voce358 found that selective oxidation of a 95Cu–5Al
Cu2O. The precise composition of the film depends, alloy by this method gave protection from atmospheric
however, on a number of factors, including tem- oxidation up to 800  C unless the film was scratched or
perature, time, and oxygen concentration in the otherwise damaged, or the atmosphere contained sulfur
atmosphere. Tylecote346 has investigated the compo- dioxide or hydrogen chloride.
sition, properties, and adherence of scales formed on The effects on oxidation resistance of copper as a
various types of copper at temperatures between 400 result of adding varying amounts of one or more
and 900  C. At the higher temperatures, the scales of aluminum, beryllium, chromium, manganese, sili-
formed on copper containing phosphorus were more con, and zirconium are described in a number of
brittle and less adherent than those formed on copper papers.360–367 Other authors have investigated the
containing no phosphorus. oxidation of copper–zinc373,374 and cupronickel
Studies have been carried out on the effects at alloys,374,375 the oxidation of copper and copper–
high temperature of sulfur349 and of atmospheres gold alloys in carbon dioxide at 1000  C376 and the
containing hydrogen sulfide,354–356 steam,357,358 sul- internal oxidation of various alloys.377–379
fur dioxide,358 and hydrogen chloride.358 Copper alloys have been used extensively in high-
pressure feed-water heaters in power generating
3.07.3.8.2 High temperature oxidation of plant.380 Experience has shown that when such hea-
copper alloys ters are operated intermittently, 70Cu–30Ni or
In the case of copper alloys which contain elements 80Cu–20Ni alloy tubes suffer fairly rapid and severe
which are more noble than copper, the resulting steam-side (external) oxidation with the formation of
surface oxide will be substantially pure copper exfoliating scales. This corrosion, which may be asso-
oxide as the oxides of the noble metals have higher ciated with ingress of air during shutdowns, has been
dissociation pressures than the copper oxides. Con- the subject of several published papers.381–385 The
versely, for alloys containing baser metals, the alloy- behavior of other alloys for feed-water heater service
ing element will appear as an oxide in the scale often has also been discussed.380,386–388
in greater concentration than in the alloy itself, and
sometimes to the exclusion of copper oxides. The
dissociation pressures of many oxides have been cal- 3.07.4 Protective Measures
culated by Lustman.359
Whether the rate of oxidation of an alloy of copper The good corrosion behavior of copper and copper
with a base metal is less or more than that of copper alloys is dependent upon correct choice of material,
will depend on the concentration of the alloying good design of equipment, and proper methods of
element and the relative diffusion velocities of operation. Brasses and bronzes may often be effec-
metal atoms or ions in the oxide layers. There is tively protected by polishing followed by periodic
extensive literature on the oxidation behavior of waxing. If proper attention is given to these factors,
copper alloys.346,347,360–367 According to Wagner’s there will usually be no need for protective measures.
theory368–371 the rate of oxidation will be largely In special cases, however, for example, to prevent the
influenced by the electrical conductivity of the film dissolution of small amounts of copper or to maintain
 Corrosion of Copper and its Alloys 1967

a high-grade finish, metallic coatings of one or more gasketing, etc., are undesirable. Occasionally the
of the following metals may be applied: tin, lead, action between different copper-based materials
nickel, silver, chromium, rhodium, or gold. In other may be appreciable particularly if the relative surface
cases painting, varnishing, or lacquering may be areas are unfavorable, for example, gunmetal may
desirable, or if the conditions are very severe (as in stimulate the corrosion of copper or brass in seawater
some corrosive soils) heavier protection such as bitu- and due care should be taken.
minous or plastic coatings may be necessary. Brasses
that are liable to suffer dezincification or stress cor-
rosion may need protection where other copper 3.07.5 Areas of Future Development
alloys would be satisfactory in an unprotected condi-
3.07.5.1 Antimicrobial Benefits of Copper
tion. Sometimes use is made of the principles of
Corrosion
cathodic protection, for example, steel ‘protector
blocks’ in condenser water-boxes. The formation of cuprous Cuþ and cupric ions Cu2þ
In some circumstances, use of inhibitors may be a has been described earlier. The ability of copper to
desirable remedial measure. For instance, benzotria- gain and lose outer electrons is the source of many of
zole (BTAH) has been found of considerable value copper’s important physical properties such as high
for preventing staining and tarnishing of copper pro- electrical and thermal conductivity, chemical stabil-
ducts.389 The characteristics of the behavior seen ity, and its reddish color. Copper ions also play a
indicate that an inhibiting film is formed by adsorp- crucial role in copper’s antimicrobial action and the
tion of neutral BTAH molecules on the copper sur- main hypotheses for the mode of actions in damaging
face followed by adsorption of a thin layer of copper the functionality of a cell of a microorganism are:
BTAH in polymeric form. Also, a synergistic effect
1. Their competing with and hindering uptake of
has been found when BTAH and iodide ions are
major minerals such as sodium and potassium.
used together to prevent copper corrosion in sulfuric
This causes serious imbalances in the mineral
acid.390 Sodium diethyldithiocarbamate also has use-
composition of the cell of the microorganism.403
ful inhibiting properties.391 Other types of inhibitors
2. Their binding to proteins inside the cell which do
can be of value in condensate systems392,393 and in
not require copper, creating a dysfunction of that
acid solutions.305–310 Reviews have been given of
protein.404,405
corrosion inhibitors for copper394 and brasses.395,396
3. Their causing oxidative damage, thereby damag-
The effects and efficiencies of various inhibitors con-
ing the cell wall and other cellular structures and
tinues to be the subject of much research.397–400 Low
finally causing bacterial cell death.406
concentrations (0.1 mM) of amino acids (glycine and
cysteine) have been demonstrated to provide over Recent work407–409 has shown the effectiveness of
95% inhibition efficiency for 95–5 cupronickel copper in inactivating pathogens such as Escherichia
corrosion.401 coli, Meticillin-resistant Staphylococcus aureus (MRSA),
The danger of accelerated attack on copper-base and Influenza A and in reducing environmental con-
materials due to coupling with other metals is small tamination in a clinical setting.410,411
in many environments since copper is usually the
cathodic member of the couple, but precautions are
3.07.5.2 Alloy Developments
often necessary to prevent excessive corrosion of the
anodic member. Surveys of the behavior of couples Cupronickel alloys in particular are being developed
involving copper and copper alloys have been for applications in seawater and oil and gas well
given.319 Titanium, high nickel alloys, and super environments. Copper nickel chrome (DEF STAN
stainless steels can be sufficiently more noble than 02-824) cast components are beginning to replace
copper alloys in seawater environments to cause gal- those made from nickel aluminum bronze when
vanic attack of the copper alloy and electrical isola- long-term seawater corrosion resistance is required.
tion or insulated spool pieces may be required. This This is due to the fact that, after 10 years of seawater
is less of a problem in chlorinated systems as preven- service, only such components have been found to
tion of the biofilm can reduce the efficiency of the have lost only 0.15 mm from their original thick-
cathode.319,402 Another material that has been found ness through corrosion, performing significantly bet-
capable of accelerating attack on copper in practice ter than cast nickel aluminum bronze under the same
is graphite; hence graphitic paints or graphite in conditions.412 Cu–Ni–Al and Cu–Ni–Sn alloys are
1968 Non-Ferrous Metals and Alloys

being developed as high strength corrosion resistant 6. Copper and Copper Alloys Compositions, Application
and Properties; Publication 120, Copper Development
alloys for seawater applications requiring hydrogen- Association: UK, 2004.
embrittlement-free, antigalling properties, and as alter- 7. The Brasses-Properties and Applications; Publication
native corrosion resistant, nonmagnetic bearing alloy to 117, Copper Development Association: UK, 2005.
8. DKI German Copper Institute Booklet: Copper nickel
Be–Cu in directional oilfield drilling equipment. alloys; Properties, Processing, Application, DKI:
Shape memory effect alloys have recently been Germany, 2000.
under development for use in electronics and den- 9. Powell, C. A.; Michels, H. T. Cupronickel Alloys for
seawater corrosion resistance and antifouling – a state of
tistry. Those based on Cu–Al and Cu–Ag–Al have the art review; Corrosion, NACE: Houston, 2000.
been found to exhibit curious electrochemical effects 10. Powell, C. Corr. Management. 2005, 63, 8.
during dissolution in alkali media if oxygen is pres- 11. DEF-STAN 02-824. Copper Nickel Chromium Sand
Castings and Ingots; UK Ministry of Defence, Abbey
ent.413 This has been explained in terms of fast pref- Wood: UK, 2002.
erential dissolution of aluminum followed by the 12. Gaffoglio, C. J. Power Eng. 1982, 60.
slow transport of aluminate ions from the surface. 13. Tuck, C. D. S.; Bendall, K. C.; Radford, G. W. J.;
Campbell, S. A.; Grylls, R. J. Paper No. 78, Corrosion/96,
This influences the formation of Cu2O, which is the NACE: Houston, 1996.
main corrosion reaction, such that an unusual oscil- 14. Ratka, J. O.; Maligas, M. N. Paper No. 04298, Corrosion
latory electro-potential effect is produced. 2004, NACE: Houston, 2004.
15. Ateya, B. G.; Elsayed, A. A.; Sayed, M. S. J. Electrochem.
Soc. 1993, 141(1), 71–78.
16. Gatty, O.; Spooner, E. C. R. Electrode Potential
Acknowledgements Behaviour of Corroding Metals in Aqueous Solutions;
Clarendon Press: Oxford, 1938.
17. Pourbaix, M. J. N. Atlas of Electrochemical Equilibria in
This section is comprised of a revised version of the Aqueous Solutions; Pergamon: Oxford, 1966.
chapter by P.T. Gilbert, which appeared in the previ- 18. Rubinic, L.; Markovic, T. Werkst. Korrosion 1959, 16, 666.
ous edition. This, in turn, was based on ‘Chemical 19. Hickling, A.; Taylor, D. Trans. Faraday Soc. 1948.
20. Kuksina, O. Y.; Kondrashin, V. Y.; Mashakov, I. K.
Properties and Corrosion Resistance of Copper and Protec. Met. (Russia) 2006, 42(2), 144.
Copper Alloys,’ which formed Chapter XVIII of the 21. Mayer, S. T.; Muller, R. H. J. Electrochem. Soc. 1992,
American Chemical Society Monograph No. 122, 139(2), 426–434.
22. Kusina, O. Y.; Kondrashin, V. Y.; Marshakov, I. K.
‘The Science and Technology of the Metal its Alloys and Protect. Met. (Russia) 2004, 40(6), 581.
Compounds,’ edited by Professor Allison Butts, and 23. Wilde, B. E.; Teterin, G. A. Br. Corros. J. 1967, 2, 125.
published by the Reinhold Publishing Corporation, 24. Mansfield, F.; Uhlig, H. H. J. Electrochem. Soc. 1970,
117, 427.
New York, in 1954. Acknowledgement is hereby 25. Varenko, E. S.; Galushko, V. P.; Kovtan, V. N.; Fedash, P. M.;
made to the Reinhold Publishing Corporation for Loshkarev, Y. M. Zashchita Metallov 1970, 6, 103.
permission to make derivations from this work. The 26. Gavgahi, M.; Kaymaz, I.; Totik, Y.; Sadeler, R. Corr. Rev.
2002, 20(4–5), 403.
revisions of the current chapter have also been con- 27. Virtanen, S.; Wojtas, H.; Schmuki, P.; Böhni, H.
tributed to by Peter Webster, Technical Consultant, J. Electrochem. Soc. 1993, 140(10), 2786–2790.
and Angela Vessey, Director, Copper Development 28. Parvizi, M. S.; Aladjem, A.; Castle, J. E. Int. Mater. Rev.
1988, 33(4), 169.
Association UK, Claes Taxén of KIMAB, Sweden and 29. Mathiyarasu, J.; Palaniswamy, N.; Muraldharan, V. S.
Rolf Sundberg of Västerås, Sweden, to whom further Corr. Rev. 2000, 18(1), 65.
acknowledgements are given. 30. Badawy, W. A.; Ismail, K. M.; Fathi, A. M. Electrochimica
Acta 2005, 50(18), 3603.
31. Vernon, W. H. J. J. Inst. Met. 1932, 49, 153.
32. Vernon, W. H. J.; Whitby, L. J. Inst. Met. 1929, 42, 181;
References 1932, 44, 389.
33. Vernon, W. H. J. Trans. Faraday Soc. 1931, 27, 255, 582.
34. Baumann, K.; Ruhrberg, U.; Kreysa, G. DECHEMA-
1. BSEN. Copper and Copper Alloys – Ingots and Castings, Werkstoffe-Tabelle, 37th Supplement (Atmosphere),
BSI: London, 1982. DECHEMA: Frankfurt, 1995.
2. CEN TC 133. CR 13388. Copper and Copper Alloys – 35. Hudson, J. C. Trans. Faraday Soc. 1929, 25, 177; J. Inst.
Compendium of composition and products, BSI: Met. 1930, 44, 409; J. Birmingham Met. Soc. 1934, 14,
London. 331; Met. Ind. 1934, 44, 415; J. Inst. Met. 1935, 56, 91.
3. EN1652. Specifications for Copper and Copper Alloys: 36. Tracy, A. W.; Thompson, D. H.; Freeman, J. R. Special
Plate, sheet, strip and circles for general purposes, EN Technical Publication No. 175; ASTM: Pittsburgh, 1955;
12163 Rod, EN12166 Wire, EN 12449 Tubes, EN12420 pp 77–87.
Forgings, BSI, London. 37. Mattsson, E.; Holm, R. Metal Corrosion in the
4. Copper and Copper Alloys; ASTM: Pittsburg, 2006. Atmosphere; STP 435; ASTM: Pittsburgh, 1968; p 187.
5. A1322. Standards Handbook for Wrought and Cast 38. Scholes, I. R.; Jacob, W. R. J. Inst. Met. 1970, 99, 272.
Copper and Copper Alloy Products; Copper 39. Morcillo, M.; Almeida, E.; Marmcos, M.; Rosales, B.
Development Association Inc., New York, 2003. Corrosion 2001, 57(11), 967.
 Corrosion of Copper and its Alloys 1969

40. Thompson, D. H. Metal Corrosion in the Atmosphere; Surface Ships and Submarines; UK Ministry of Defence,
STP 435; ASTM: Pittsburgh, 1968; p 129, 199. Abbey Wood, 2009.
41. Holm, R.; Mattsson, E. Atmospheric Corrosion of Metals; 77. Kirk, W. Evaluation of Critical Seawater Hydrodynamic
STP 767; ASTM: Pittsburgh, 1982; p 85. Effects of Erosion Corrosion of CuNi, INCRA Report 396
42. Ramos, A. C.; Camoes, M. F.; Mendonca, M. H.; 1987.
Foneca, I. I. E. Corr. Prot. Mater. 2001, 20(4), 16. 78. Beckmann, W.; Hecht, M.; Jasner, M.; Steinkemp, K.
43. Tracy, A. W. STP No. 175; ASTM: Pittsburgh, 1955; Kuala Lumpur Fabrication Technology Corrosion
pp 67–76. 2001, Kuala Lumpur; Institute of Materials: London,
44. Tidblad, J.; Leygraf, C.; Kucera, V. J. Electrochem. Soc. 2000.
1991, 138(12), 3592–3598. 79. LaQue, F. L. Proc. Am. Soc. Test. Mater. 1952, 52, 1.
45. Eriksson, P.; Johansson, L.-G.; Strandberg, H. J. 80. Evans, U. R. J. Electrochem. Soc. 1939, 75, 446;
Electrochem. Soc. 1993, 140(1), 53–59. Fink, F.W. J. Electrochem. Soc. 1939, 75, 446, 441.
46. Strandberg, H.; Johansson, L.-G. J. Electrochem. Soc. 81. Lucey, V. F. Br. Corr. J. 1965, 1(9), 53.
1998, 145(4), 1093. 82. Feller, H.-G. Z. Metallkunde 1967, 58, 875.
47. Knotkova, D. Proceedings of 12th International Corrosion 83. Heidersbach, R. Corrosion 1968, 24, 38.
Congress, Houston; NACE: Houston; Sept 1993; Vol. 2, 84. Kenworthy, L.; O’Driscoll, W. G. Corr. Technol. 1955, 2,
p 51. 247.
48. Laub, H. Metallurgy 1968, 22, 1116. 85. Piatti, L.; Grauer, R. Werkst. Korrosion 1963, 14, 551.
49. Veleve, L.; Luja, M. Br. Corr. J. 1999, 34(1), 34. 86. Hashimoto, K.; Ogawa, S.; Shimodaira, S. Trans. Jpn.
50. Hullman, H. Proceedings of UN ECE Workshop, Munich, Inst. Met. 1963, 4, 42.
May 2003; Swedish Corrosion Institute, Stockholm, 2003. 87. Sugawara, H.; Ebiko, H. Corr. Sci. 1967, 7, 513.
51. Priggemeyer, S. Report AZ 10730, Deutsche 88. Joseph, G.; Arce, M. T. Corr. Sci. 1967, 7, 597.
Bundesstiftung Umwelt; 1998. 89. Langenegger, E. E.; Robinson, F. P. A. Corrosion 1968,
52. Priggemeyer, S.; Priggemeyer, S. Metallurgy 1999, 53, 24, 411; 1969, 25, 59.
204. 90. Horton, R. M. Corrosion 1970, 26, 160.
53. Leuenberger-Minger, A. U.; Faller, M.; Richner, P. Mat. 91. Rothenbacher, P. Corr. Sci. 1970, 10, 391.
Corr. 2002, 54(3), 157. 92. Pötzl, A.; Lieser, K. H. Z. Metallkunde 1970, 61, 527.
54. UN ECE-Report. Investigation of the Metal Run-off from 93. Sundberg, R.; Holm, R.; Hertzman, S.; Hutchinson, B.;
Copper Surfaces exposed to Atmosphere; Bulletin – Lindh-Ulmgren, E. Metallurgy 2003, 57, 721.
Korrosions Institutet, 2003, ISSU 109E. 94. Hutchinson, B.; Oliver, J.; Lindh-Ulmgren, E.;
55. Odnevall Wallinder, I.; Leygraf, C. J. Corr. Sci. 1997, 39, Symniotis, E. In Investigation into the Dezincification of
2039. a-Brass; Proceedings of the International Conference
56. Bertling, S.; Odnevall Wallinder, I.; Berggren Kleja, D.; Copper 2006; Welter, J.-M. Ed.; Wiley-VHC, 2006.
Leygraf, C. Environ. Toxicol. Chem. 2006, 25, 891. 95. Bengough, G. D.; Jones, R. M.; Pirret, R. J. Inst. Met.
57. Odnevall Wallinder, I.; Bahar, B.; Leygraf, C.; Tidblad, J. 1920, 23, 65.
J. Environ. Monit. 2007, 9, 66. 96. Upton, B. Br. Corros. J. 1966, 1, 134.
58. Sandberg, I.; Odnevall Wallinder, I.; Leygraf, C.; 97. Baldwin, A. B.; Campbell, H. S. Brit. Waterworks
Le Bozec, N. J. Corr. Sci. 2006, 39, 4316. Assoc. J. 1961, 43, 13.
59. Karlén, C.; Odnevall Wallinder, I.; Heijerick; Leygraf, C. 98. Schafer, G. J.; Dall, R. A. Aust. Corr. Eng. 1966, 10, 39.
Environ. Pollut. 2002, 120, 691. 99. Ladeburg, H. Metallurgy 1966, 20, 33.
60. Odnevall Wallinder, I.; Leygraf, C. J. Corr. Sci. 2001, 43, 100. Simmonds, M. A.; Huxley, W. G. S. Aust. Corr. Eng. 1967,
2379. 11, 9.
61. Odnevall Wallinder, I.; Verbiest, P.; He, W.; Leygraf, C. J. 101. Bengough, G. D.; May, R. J. Inst. Met. 1924, 32, 81;
Corr. Sci. 2000, 42, 1471. Discussion of Bradbury, E. J.; Johnson, L. W. Trans. Inst.
62. Sundberg, R. Metallurgy 2005, 59, 10. Mar. Engrs. 1951, 63, 59.
63. Arnold, R. Integrat. Environ. Assess. Mgmt. 2005, 1, 333. 102. Breckon, C.; Gilbert, P. T. Chem. Ind. 1964, 4, 35.
64. Boulanger, B.; Nikolaidis, N. P. J. Am. Water Resources 103. Bem, R. S. The Engineer 1958, 206, 756.
Assn. 2003, 39, 325. 104. Sundberg, R.; Hertzman, S.; Linder, M. In Intergranular
65. Romanoff, M. Underground Corrosion; Nat. Bur. Stand. Corrosion (IGA) of Brass; Proceedings of the International
Circ. 579; Supt.of Documents: Washington, D.C, 1957. Conference Copper 2006 Welter, J.-M. Ed.; Wiley-VHC,
66. Gilbert, P. T. J. Inst. Met. 1947, 7, 139. 2006.
67. Gilbert, P. T.; Porter, F. C. Iron and Steel Institute Special 105. Mazza, F.; Torchio, S. J. Corr. Sci. 1983, 23, 1053.
Report No. 45, 1952, pp 55–74, pp 127–134. 106. Tumer, M. E. D. Proc. Soc. Water Treatm. Exam. 1961,
68. Markovic, T.; Sevic, M.; Rubinic, L. Werkst. Korrosion 10, 162; 1965, 14, 81.
1960, 11, 87. 107. Clark, W. D. J. Inst. Met. 1947, 73, 263.
69. Maeda, M.; Tenyama, K.; Shibayanagi, T.; Naka, M. 108. Breckon, C.; Gilbert, P. T. Proceedings of the first
Mater. Charac. 2005, 55(2), 127. International Congress on Metal Corrosion, London;
70. Angelini, E.; Mongiatti, A.; Grassini, S.; Rosalbino, F.; Butterworths: London, 1962; p 624.
Ingo, G. M.; De Caro, T. EUROCORR 2004, Nice, Sept 109. Meigh, H. Cast and Wrought Aluminum Bronzes –
2004. Published CEFRACOR: Paris, 2004. Properties, Processes and Structure; IOM
71. Efird, K. D. Corrosion 1977, 33(1), 347. Communications, 2000.
72. Obrecht, M. F. Corrosion 1962, 18, 189t. 110. Brezina, P. Int. Met. Rev. 1982, 27(2), 1.
73. Solelev, A. J. Inst. Wat. Engrs. 1955, 9, 208. 111. Weill-Couly, P.; Arnoud, D. Fonderie 1973, 322.
74. Gilbert, P. T. Br. Corr. J. 1979, 14, 20. 112. Taxen, C. Korrosioninstitutet Rapport 1996, 8, 1.
75. Aluminium Bronze Alloys Corrosion Resistance Guide; 113. Campbell, H. S. Chem. Ind. 1955, 692.
Publication 80, Copper Development Association, UK, 114. Hatch, G. B. J. Am. Waterworks Assn. 1961, 53, 1417.
1981. 115. Hatch, G. B. NACE Tech. Rep. 60–11; Corrosion 1960,
76. Defence Standard 01-782. Protection of Seawater 16, 453t.
System Pipework and Heat Exchanger Tubes in HM 116. Schafer, G. J. New Zealand J. Sci. 1962, 5, 475.
1970 Non-Ferrous Metals and Alloys

117. Lucey, V. F. Br. Corr. J. 1967, 2, 175. Johnson, L.; Poirier, K. A. Regulat. Toxicol. Pharmacol.
118. Campbell, H. S. Proceedings of the second International 2001, 34, 137–145.
Congress on Metal Corrosion, New York (1963); NACE: 149. Davenport, W. H.; Nole, V. F.; Robertson, W. D.
Houston, 1966; p 237. J. Electrochem. Soc. 1959, 106, 1005.
119. Gilbert, P. T. Aust. Corr. Eng. 1969, 13, 513. 150. Ives, D. J. G.; Rawson, A. E. J. Electrochem. Soc. 1962,
120. Zhu, X.; Lei, T. J. Mat. Sci. Technol. (China) 1998, 109, 447.
14(1), 57. 151. Obrecht, M. F.; Pourbaix, M. J. Am. Waterworks Assoc.
121. Lin, L.; Lui, S.; Lui, Z.; Xu, J. Corr. Sci. Protect. Technol. 1967, 59, 977.
1999, 11(1), 37. 152. Grunau, E. B. Städtehygiene 1967, 7, 153.
122. Sundberg, R. Metallurgy 2002, 56(11), 714. 153. Tuthill, A. H. Mater. Perfor. 1987, 26(9), 12.
123. Schafer, G. J.; Dall, R. A. Aust. Corr. Eng. 1963, 7(10), 33. 154. Defence Standard 01/2 and Angell, B.; Tuck, C. D. S.,
124. Proceedings of the International Corrosion of Copper & private communications, UK Ministry of Defence,
Copper Alloys in Building; Tokyo, Japanese Copper Bristol, UK.
Development Association, 1982. 155. Shone, E.; Grim, G. Trans I. Mar. Eng. 1976, 98, Paper 11.
125. Cornwall, F. J.; Wildsmith, G.; Gilbert, P. T. Br. Corr. J. 156. Kirk, W.; Tuthill, A. The Application of Copper Nickel
1973, 8, 202. Alloys in Marine Systems. Copper Nickel Condenser and
126. Oliphant, R. J. Causes of Copper Corrosion in Heat Exchanger System, CDA Inc Seminar Technical
Plumbing Systems; Foundation for Water Research, Report 7044–1919, CDA, Inc: New York, 1992.
2003. 157. Jasner, M.; Hecht, M.; Beckman, W. Heat Exchangers
127. Mattson, E.; Fredriksson, A.-M. Br. Corr. J. 1968, 3, 246. and Piping Systems from Copper Alloys –
128. Mattson. E., Werkst. U Korros. 1988, 39, 499. Commissioning, Operating and Shutdown; KME:
129. Linder, M. Proceedings of the 9th Scandinavian Osnabruck, 1998.
Corrosion Congress, Copenhagen, 1983, pp 569–581. 158. Gilbert, P. T. Conference of Historical Metallurgy Society,
130. Drogowska, M.; Brossard, L.; Menard, H. Birmingham, Paper Copper 4, 1984.
J. Electrochem. Soc. 1992, 139(1), 39–47. 159. Powell, C. A.; Michels, H. T. Cupronickel Alloys for
131. Milosev, I.; Metikos-Hukovic, M.; Drogowska, M.; seawater corrosion resistance and antifouling – A State of
Menard, H.; Brossard, L. J. Electrochem. Soc. 1992, the Art review; Corrosion 2000; NACE: Houston, 2000.
139(9), 2409–2418. 160. Zhu, X.; Lin, L.; Lei, T. Acta Metall. Sinica (China) 1997,
132. Drogowska, M.; Brossard, L.; Menard, H. 33(12), 1256.
J. Electrochem. Soc. 1993, 140(5), 1247–1251. 161. Zhu, X.; Lin, L.; Xu, J.; Lei, T. Chin. J. Non-ferrous Met.
133. BSEN 12502:2004. Protection of metallic materials 1997, 7(2), 79.
against corrosion. Guidance on the assessment of 162. Nicklin, G. J. E. Living with the threat of microbiologically
corrosion likelihood in water distribution and storage influenced corrosion in submarine seawater systems-the
systems. Influencing factors for cast iron, unalloyed and Royal Navy’s perspective. Proceedings of 9th
low alloyed steels and BSEN 14868:2005, Protection of International Naval Engineering Conference (INEC 2008),
Metallic Materials against Corrosion. Guidelines on the Hamburg, IMarEST, London, 2008.
assessment of corrosion likelihood in closed water 163. Schleich, W. Corrosion 2005; NACE: Houston, 2005,
circulation systems, BSI, UK, 2005. Paper No. 5222.
134. Rogers, T. H. J. Inst. Met. 1948, 75, 19–38. 164. Theile, E. W. Proceedings of CDA Heat Exchanger
135. Keevil, C. W.; Walker, J. T.; McAvoy, J.; Colbourne, J. S. Seminar; New York, April; Copper Development
In Biocorrosion; Gaylarde, C. C., Moreton, L. H. G., Eds.; Association: New York, 1981.
Biodeterioration Society: Kew, 1988. 165. Sato, S. Proceedings of the fourth International
136. Wagner, D.; Fischer, W.; Tuschewitzki, G. J. Congress of Metal Corrosion Amsterdam, 1969; NACE:
Microbiologically influenced corrosion of copper pipes Houston, 795, 1972.
Final report, ICA project number 453, 1992. 166. i,s Lee, T. S. Pre-treatment of Condenser Tubing for
137. Geesey, G. G; Mittleman, M. W.; Iwaoka, T.; Griffiths, P. R. Enhanced Corrosion Resistance; INCRA Project 284
Materials Performance 1986, 37–40. Final Report, NiDI, 1985.
138. Geesey, G. C.; Lewandowski, Z.; Fleming, H.-C. 167. Rowlands, J. C. J. Appl. Chem. 1965, 15, 57.
Biofouling/Biocorrosion in Industrial Water Systems; 168. Lemieux, E.; Wolejsza, T. M.; Grolleau, A. M. Corrosion
Lewis Publishers: Chelsea, MI, 1993. 2002; Denver; NACE: Houston, 2002, Paper No. 02210.
139. Tronstad, R.; Veimo, R. J. Inst. Met. 1940, 66, 17. 169. Berthagen, L. The use of Cathodic Protection for Copper
140. Kenworthy, L. J. Inst. Heat. Vent. Engst. 1940, 8, 15. Alloys in Seawater Cooling Systems, EFC Working Party
141. Gilbert, P.T. Proc. Soc. Water Treatm. Exam. 1966, Report, EuroCorr 2001, Maney Publishing: London, 2001.
15, 165. 170. Tuthill, A. H.; Todd, B.; Oldfield, J. IDA World Congress
142. Priggemeyer, St.; Priggemeyer, S.; Meyer, E.; Sauter, W.; on Desalination and Water Reuse; Madrid 1997; Vol. IIIp
Breu, M.; Schüz, G.; Arens, P.; Baukloh, A. In Copper 251p 25, paper No. 73.
Release of Copper Tubes in Contact with Hard Drinking 171. Oldfield, J. W.; Todd, B. A Review of Materials and
Waters, Conference Proceedings of CEOCOR Plenary Corrosion in Desalination-Key Factors for Plant
Meeting 2001; Biarritz. Reliability; IDA World Congress on Desalination and
143. Critchley, M.; Taylor, R.; O’Halloran, R. Mater. Perform. Water Science: Abu Dhabi, 1995.
2005, 44(6), 56. 172. Gilbert, P. T.; Jenner, B. J. International Marine and Shipping
144. Merkel, T. H.; Pehkonen, S. O. Corr. Eng. Sci. Technol. Conference; Institute of Marine Engineers: London, 1969.
2006, 41(1), 21–37. 173. Li, W.; Lui, D.; Wei, K. Corr. Sci. Protect. Technol. 1995,
145. Kenworthy, L. J. Inst. Met. 1943, 69, 67. 7(3), 232.
146. Porter, F. C.; Hadden, S. E. J. Appl. Chem. 1953, 3, 385. 174. Sigh, I.; Basu, D. K.; Singh, M. N.; Battamishra, A. K. Anti-
147. Guidelines for Drinking Water Quality, 3rd ed.; WHO: Corrosion Meth. Mat. 1993, 44(3), 195.
Geneva, 2008. 175. Nelson, G. A. Bull. Am. Soc. Test. Mat. 1959, 240, 39.
148. Araya, M.; McGoldrick, M. C.; Klevay, L. M.; Strain, J. J.; 176. Agarwal, D. C. Br. Corr. J. 2002, 37(2), 105.
Robson, P.; Nielsen, F.; Olivares, M.; Pizarro, F.; 177. Agarwal, D. C. Corr. Eng. Sci. Technol. 2003, 38(4), 275.
 Corrosion of Copper and its Alloys 1971

178. Agarwal, D. C.; Sarin, S.; Wadhura, R.; Vishwakarma, R.; 219. McEvily, A. J., Jr.; Bond, A. P. J. Electrochem. Soc. 1965,
Deshmukh, M. B.; Kurian, S. J. Failure Anal. Prev. 2005, 112, 131.
5, 70. 220. Forty, A. J. Met. Progr. 1959, 75, 154.
179. Slusser, J. W.; Dean, S. W.; Drummer, D. M. Corrosion 221. Graf, L.; Lacour, H. R. Z. Metallk. 1960, 51, 152; 1962,
’86 NACE: Houston, 1986, Paper 330. 53, 764.
180. Parkins, R. N.; Holroyd, N. J. H. Corrosion 1982, 222. Graf, L.; Richter, W. Z. Metallk. 1961, 52, 834.
38, 245. 223. Aebi, F. Z. Metallk. 1955, 46, 547; 1956, 47, 421.
181. Robertson, W. D. Trans. Amer. Inst. Min. (Metall.) Engrs. 224. Bakish, R.; Robertson, W. D. J. Electrochem. Soc. 1956,
1951, 191, 1190. 103, 320.
182. Edmunds, G. Symposium on Stress-corrosion Cracking 225. Edeleanu, C.; Forty, A. J. Philos. Mag. 1960, 5(58),
in Metals; ASTM: Philadelphia, 1944; pp 67–89. 1029.
183. Elliot, P.; Corbett, R. A. In Corrosion/1999 NACE: 226. Graf, L. Metallurgy 1964, 18, 1163, 17.
Houston, 1999, Paper No. 342. 227. Lynes, W. Corrosion 1965, 21, 125.
184. Wilson, T. C.; Edmunds, G.; Anderson, E. A.; Peirce, W. M. 228. Pugh, E. N.; Westwood, A. R. C. Philos. Mag. 1966,
Symposium on Stress-corrosion Cracking in Metals; 13, 167.
ASTM: Philadelphia, 1944; pp 173–193. 229. Pugh, E. N.; Montague, W. G.; Westwood, A. R. C. ASM.
185. Sato, S.; Nosetani, T. Sumitomo Light Metal Tech. Rep. Trans. Quart. 1965, 58, 665.
1969, 10(2), 83. 230. Hoar, T. P.; Booker, C. J. L. Corr. Sci. 1965, 5, 821.
186. Syrett, B. C.; Parkins, R. N. Corr. Sci. 1970, 10, 197. 231. Fairman, M. Corr. Sci. 1966, 6, 37.
187. Uhlig, H. H. Ed. Corrosion Handbook; Wiley: New York, 232. Takano, M.; Shimodaira, S. Corr. Sci. 1968, 8, 55.
1948; pp 78–79. 233. Lahiri, A. K. Br. Corr. J. 1968, 3, 289.
188. Sato, S. Sumitomo Light Met. Tech. Rep. 1960, 1(3), 45. 234. Lahiri, A. K.; Banerjee, T. J. Corr. Sci. 1968, 8, 895.
189. Kamath, K. V.; Erdmann-Jesnitzer, F. Metallurgy 1960, 235. Hoar, T. P.; Rothwell, G. P. Electrochim. Acta 1970,
14, 1061. 15, 1037.
190. Thompson, D. H. Chem. Eng. 1961, 68(3), 130. 236. Swann, P. R.; Nutting, J. J. Inst. Met. 1960, 88, 478.
191. Laub, H. Metallurgy. 1966, 20, 1174. 237. Swann, P. R. Corrosion 1963, 19, 102t.
192. Adamson, K. Corr. Sci. 1967, 7, 537. 238. Swann, P. R.; Pickering, H. W. Corrosion 1963, 19, 369t,
193. Erdmann-Jesnitzer, F.; Kacslingk, N. Werkst. Korrosion 373t.
1969, 20, 493. 239. Tromans, D.; Nutting, J. Corrosion 1965, 21, 143.
194. Copper Alloys-ammonia test for stress corrosion 240. Brown, B. F. Met. Mater. 1968, 2(12), 171.
resistance, ISO 6957; BSI: London, 1988. 241. Graf, L. Werkst. Korrosion 1969, 20, 408.
195. Wrought copper and copper alloys. Detection of residual 242. Robertson, W. D. Ed. Stress Corrosion Cracking and
stress. Mercurous nitrate test, ISO 196; BSI: London, 1995. Embrittlement (Electrochem. Soc. Symposium); Wiley:
196. Helling, S.; Lissner, O.; Rask, S.; Ström, B. Werkst. New York, 1956.
Korrosion 1957, 8, 569. 243. Rhodin, T. N. Ed. Physical Metallurgy of Stress-Corrosion
197. Aebi, F. Z. Metallk. 1958, 49, 63. Fracture (AIME Symposium); Interscience: New York,
198. Thompson, D. H. Mater. Res. Standards 1961, 1, 108. 1959.
199. Szabo, E. Werkst. Korrosion 1963, 14, 162. 244. Conference on Fundamental Aspects of Stress
200. Mattsson, E.; Lindgren; Rask, S.; Wennström, G. Current Corrosion Cracking, Ohio State University, 1967; NACE:
Corrosion Research in Scandinavia; Kemian Houston, 1969.
Keskususliitto: Helsinki, 1965; p 171. 245. Bailey, A. R. Metall. Rev. 1961, 6(21), 101.
201. Baumann, G. Werkst. Korrosion 1962, 13, 737. 246. Sparks, J. M.; Scully, J. C. J. Corr. Sci. 1974, 16, 619.
202. Sato, S. Sumitomo Light Metal Tech. Rep. 1963, 4(1), 48. 247. Kermani, M.; Scully, J. C. J. Corr. Sci. 1978, 18, 833;
203. Uhlig, H. H.; Sansone, J. Mater. Protection 1964, 3(2), 21. 1979, 89, 489.
204. Peters, B. F.; Carson, J. A. H.; Barer, R. D. Mater. 248. Scully, J. C. Met. Sci. 1978, 12, 290; J. Corr. Sci. 1980,
Protect. 1965, 4(5), 24. 20, 297.
205. Logan, H. L.; Ugiansky, G. M. Mater. Protect. 1965, 249. Takano, M.; Staehle, R. W. Trans. Jpn. Inst. Met. 1978,
4(5), 79. 19, 1.
206. Laub, H. Metallurgy 1966, 20, 597. 250. Takano, M. Trans. Jpn. Inst. Met. 1977, 18, 787.
207. Laub, H. Metallurgy 1967, 21, 173. 251. Takano, M. Corrosion 1974, 30, 441.
208. Laub, H. Metalloberfläche 1966, 20, 413, 453, 493. 252. Kawashima, A.; Agrawal, A. K.; Staehle, R. W. Spec.
209. Sato, S.; Nosetani, T. Sumitomo Light Metal Tech. Rep. Tech. Pub. 1979, 665, 266.
1969, 10(3), 175. 253. Uhlig, H.; Gupta, K.; Liang, W. J. Electrochem. Soc.
210. Whitaker, M. E. Metal. Manchr. 1948, 39, 21, 66. 1975, 122, 343.
211. Perryman, E. C. W.; Goodwin, R. J. J. Inst. Met. 1954, 254. Holroyd, N. J. H.; Hardie, D.; Pollock, W. J. Br. Corr. J.
13, 378. 1982, 17, 103.
212. Bailey, A. R. J. Inst. Met. 1959, 87, 380. 255. Logan, H. L. Meta. Eng. Quart. 1965, 5, 32.
213. Sheehan, T. L.; Dickerman, H. E. J. Am. Soc. Nav. Engrs. 256. Parkins, R. N. Metall. Rev. 1964, 9(35), 201.
1946, 58, 586. 257. Engel, H.-J.; Speidel, M. O. Werkst. Korrosion 1969,
214. Evans, U. R. Symposium on Internal Stresses in 20, 281.
Metals and Alloys; Institute of Metals: London, 1947; 258. Thompson, D. H.; Tracy, A. W. J. Met. N.Y. 1949, 1,
pp 291–310. 100.
215. Pugh, E. N.; Craig, J. V.; Montague, W. G. ASM. 259. Pugh, E. N.; Montague, W. G.; Westwood, A. R. C. Corr.
Trans. Quart. 1968, 61, 468. Sci. 1966, 6, 345.
216. Mattsson, E. Electrochim. Acta 1961, 3, 279. 260. Uhlig, H. H.; Duquette, D. J. J. Corr. Sci. 1969, 9, 557.
217. Forty, A. J.; Humble, P. Philos. Mag. 1963, 8(86), 247. 261. White, L. F.; Blazey, C. Met. Ind. 1949, 75, 92.
218. Proceedings of the Second International Conference of 262. Sylwestrowicz, W. D. Corrosion 1969, 25, 168, 405;
Metal Corrosion, New York (1963); NACE: Houston, 1970, 26, 160.
1966; p 80. 263. Lahiri, A. K.; Banerjee, T. Corr. Sci. 1965, 5, 731.
1972 Non-Ferrous Metals and Alloys

264. Chatterjee, U. K.; Sircar, S. C.; Banerjee, T. Corrosion 310. Desai, M. N.; Shah, Y. C.; Punjani, B. K. Br. Corr. J. 1969,
1970, 26, 141. 4, 309.
265. Chatterjee, U. K.; Sircar, S. C. Br. Corros. J. 1970, 5, 128. 311. Ammar, I. A.; Riad, S. Corr. Sci. 1969, 9, 423.
266. Blackwood, A. W.; Stoloff, N. S. ASM. Trans. Quart. 312. Desai, M. N.; Rana, S. S. Werkst. Korrosion 1966, 17,
1969, 62, 677. 870.
267. Harry Meigh. Cast and Wrought Aluminum 313. Radley, J. A.; Stanley, J. S.; Moss, G. E. Corr. Technol.
Bronzes-Properties, Processes and Structure; IOM 1959, 6, 229.
Communications, 2000. 314. Schaefer, B. A. Corr. Sci. 1968, 8, 623.
268. Helliwell, B. J.; Williams, K. J. Metallurgia 1970, 81, 131. 315. Bartoniček, R.; Holinka, M.; Lukašovská, M. Werkst.
269. Nishimara, R.; Yoshida, T. Corr. Sci. 2008, 50(4), 1205. Korrosion 1968, 19, 1032.
270. Thompson, D. H. Corrosion 1959, 15, 433t. 316. Green, J. A. S.; Mengelberg, H. D.; Yolken, H. T. J.
271. Marshall, T.; Hugil, A. J. Corrosion 1957, 13, 329t. Electrochem. Soc. 1970, 117, 433.
272. Klement, J. F.; Maersch, R. E.; Tully, P. A. Corrosion 317. Jenkins, L. H.; Durham, R. B. J. Electrochem. Soc. 1970,
1959; 15p 295t. 117, 768.
273. Norden, R. B. Chem. Eng. 1958, 65, 194, 196. 318. Dubrisay, R.; Chesse, G. Comp. Rend. Acad. Sci. Paris
274. Klement, J. F.; Maersch, R. E.; Tully, P. A. Met. Prog. 1945, 220, 707.
1959, 75, 82; Corrosion, 1960, 16, 519t; U.S. Pat. 2 829 319. Francis, R. The Selection of Materials for Seawater
972. Cooling Systems – A Practical Guide for Engineers;
275. Robertson, W. D.; Grenier, E. G.; Davenport, W. H.; NACE Publication, 2006.
Nole, V. F. Met. Prog. 1959, 75, 152; U.K. Pat. 802 044. 320. Campbell, S. A.; Radford, G. J. W.; Tuck, C. D. S.;
276. Andersen, M. W.; Joosten, M.; Murali, J.; Milliams, D. E. Barker, B. D. Corrosion 2002, 58(1), 57.
Corrosion/96; NACE: Houston, 1996, Paper No. 78. 321. Reichert, J. S.; Pete, R. H. Chem. Eng. 1947, 54, 218.
277. Tuck, C. D. S. Corrosion 2005; NACE: Houston, 2005, 322. West, J. R. Chem. Eng. 1951, 58, 281.
Paper No. 5462. 323. Botham, G. H.; Dummett, G. A. J. Dairy Res. 1949, 16, 23.
278. El Domiaty, A.; Alhajji, J. N. J. Mat. Eng. Perform. 1997, 324. Holness, H.; Ross, T. K. J. Appl. Chem. 1951, 1, 158.
6(4), 534. 325. Bukowiecki, A. Schweizer Archiv. Angew. Wiss. 1958,
279. Pound, B. G. Corrosion 1994, 50(4), 301. 24, 355.
280. Lee, J. A. Materials of Construction for Chemical Process 326. Mason, J. F. Corrosion 1948, 4, 305.
Industries; McGraw-Hill: New York, 1950. 327. Inglesent, H.; Storrow, J. A. J. Soc. Chem. Ind. 1945,
281. Rabald, E. Corrosion Guide; Elsevier: New York, 1951. 64, 233.
282. LaQue, F. L. Corrosion 1954; 10p 391. 328. Clendenning, K. A. Canad. J. Res. F (Technol.) 1948,
283. Heim, A. T. Ind. Eng. Chem. 1957, 49, 63A, 64A, 66A. 26, 277.
284. Baker, S. Corr. Technol. 1961, 8, 8. 329. Mimura, K.; Lim, J.-W.; Isshika, M.; Zhu, Y.; Jiang, Q.
285. Tracy, A. W. Chem. Eng. 1962, 69, 130, 152. Met. Mat. Trans. A 2006, 37(4), 1231.
286. Gould, A. J.; Evans, U. R. J. Iron Steel Inst. 1947, 155, 330. Vernon, W. H. J. Chem. Ind. (Rev.) 1940, 59, 87.
195. 331. Kubaschewski, O.; Hopkins, B. E. Oxidation of Metals
287. Lacan, M.; Markovic, T.; Rubinic, L. Werkst. Korrosion and Alloys; Butterworths: London, 1953.
1959, 10, 767. 332. Hauffe, K. Oxydation von Metallen und Legierungen;
288. Holmberg, M. E.; Prange, F. A. Ind. Eng. Chem. 1945, 37, Springer-Verlag: Berlin, 1956.
1030. 333. Wagner, C.; Grunewald, K. Z. Phys. Chem. 1938, 40, 455.
289. Lingnau, E. Werkst. Korrosion 1957, 8, 216. 334. Dighton, A. L.; Miley, H. A. Trans. Electrochem. Soc.
290. Fontana, M. G. Ind. Eng. Chem. 1950, 42, 69A. 1942, 81, 321.
291. Groth, V. J.; Hafsten, R. J. Corrosion 1954, 10, 368. 335. Evans, U. R. Trans. Electrochem. Soc. 1947, 91, 547.
292. Bulow, C. L. Chem. Eng. 1946, 53, 210. 336. Evans, U. R. Res. Lond. 1953, 6, 130.
293. Friend, W. Z.; Mason, J. F. Corrosion 1949, 5, 355; NACE, 337. Mott, N. F. Trans. Faraday Soc. 1939, 35, 1175; 1940, 36,
Report; Corrosion 1957, 13, 757t. 472; 1947, 43, 429.
294. Russell, R. P.; White, A. Ind. Eng. Chem. 1927, 338. McKewan, W.; Fassell, W. M. J. Met. M. Y. 1953, 51,
19, 116. 1127.
295. Damon, G. H.; Cross, R. C. Ind. Eng. Chem. 1936, 339. Paidassi, J. Acta Metall. 1958, 6, 216.
29, 231. 340. Lohberg, K.; Wolstein, P. Z. Metallk. 1955, 46, 734.
296. Cornet, I.; Barrington, E. A.; Behrsing, G. U. 341. Baur, J. P.; Bridges, D. W.; Fassell, W. M.
J. Electrochem. Soc. 1961, 108, 947. J. Electrochem. Soc. 1956, 103, 273.
297. Caney, R. J. T. Aust. Eng. 1954, 64, 54; U.K. Pat 718,987. 342. Gulbrausen, E. A.; Copan, T. P.; Andrew, K. F.
298. Zitter, H.; Kraxner, G. Werkst. Korrosion 1963, 14, 80. J. Electrochem. Soc. 1961, 108, 119.
299. Piatti, L.; Fot, E. Werkst. Korrosion 1964, 15, 27. 343. Ro¨nnquist, A. J. Inst. Met. 1962, 91, 89.
300. Gregory, D. P.; Riddiford, A. C. J. Electrochem. Soc. 344. Yoda, E.; Siegel, B. M. J. Appl. Phys. 1963, 34, 1512.
1960, 107, 950. 345. Wallwork, G. R.; Smeltzer, W. W. Corr. Sci. 1969, 9, 561.
301. Talati, J. D.; Desai, M. N.; Trivedi, A. M. Werkst. Korrosion 346. Tylecote, R. F. J. Inst. Met. 1950, 78, 327; 1952, 81, 681.
1961, 12, 422. 347. Bardeen, J.; Brattain, W. H.; Shockley, W. J. Chem. Phys.
302. Graydon, W. F. J. Electrochem. Soc. 1962, 109, 1130. 1946, 14, 714.
303. Kagetsu, T. J.; Gradon, W. F. J. Electrochem. Soc. 1963, 348. Castellan, G. W.; Moore, W. J. J. Chem. Phys. 1949,
110, 856. 17, 41.
304. Feller, H.-G. Corr. Sci. 1968, 8, 259. 349. Tylecote, R. F. J. Inst. Met. 1950, 78, 301.
305. Otsuka, R.; Uda, M. Corr. Sci. 1969, 9, 703. 350. Pilling, N. B.; Bedworth, R. E. J. Inst. Met. 1923, 19, 529.
306. Rana, S. S.; Desai, M. N. Indian J. Technol. S 1967, 393. 351. Feitknecht, W. Z. Elektrochem. 1929, 35, 142, 500.
307. Desai, M. N.; Shah, Y. C. Anti-Corr. Meth. Mater. 1968, 352. Vernon, W. H. J. J. Chem. Soc. 1926, 2273.
15(12), 9. 353. Valensi, G. Pittsburgh International Conference on
308. Desai, U.; Gandhi, M. H. Corr. Sci. 1969, 9, 65. Surface Reactions; Corrosion Publishing: Pittsburgh,
309. Padma, D. K. Anti-Corr. Meth. Mater. 1969, 16, 4. 1948; pp 156–165.
 Corrosion of Copper and its Alloys 1973

354. Oudar, J. Metaux 1960, 35, 397, 445. 390. Wu, Y. C.; Zhang, P.; Pickering, H. W.; Allara, D. L.
355. Dyess, J. B.; Miley, H. A. Trans. Am. Inst. Min. (Metall.) J. Electrochem. Soc. 1993, 140(10), 2791–2800.
Eng. 1939, 133, 239. 391. Bhatt, I. M.; Soni, K. P.; Triveda, A. M. Werkst. Korrosion
356. Vernon, W. H. J. Trans. Faraday Soc. 1924, 19, 839. 1967, 18, 968.
357. Preston, G. D.; Bircumshaw, L. L. Philos. Mag. 1935, 392. Tinley, W. H. Chem. Ind. 1964, 12, 2036.
20, 706. 393. Obrecht, M. F. Proceedings of the Second International
358. Hallowes, A. P. C.; Voce, E. Metal. Manchr. 1946, 34, 95. Congress on Metal Corrosion, New York (1963); NACE:
359. Lustman, B. Met. Prog. 1946, 50, 850. Houston, 1966; p 624.
360. Dennison, J. P.; Preece, A. J. Inst. Met. 1952, 81, 229. 394. Desai, M. N.; Rana, S. S.; Gandhi, M. H. Anti-Corr.
361. Blade, J. C.; Preece, A. J. Inst. Met. 1959, 88, 427. Methods Mater. 1970, 17(6), 17.
362. Maak, F.; Wagner, C. Werkst. Korrosion 1961, 12, 273. 395. Desai, M. N.; Shah, Y. C.; Gandhi, M. H. Aust. Corros.
363. Wallbaum, H. J. Werkst. Korrosion 1961, 12, 417. Eng. 1968, 12(3), 3.
364. Maak, F. Z. Metallkunde 1961, 52, 538. 396. Desai, M. N.; Shah, Y. C. Werkst. Korrosion 1970, 21,
365. Zwicker, U. Metallurgy 1962, 16, 1110. 712.
366. Kapteijn, J.; Couperus, S. A.; Meijering, J. L. Acta Metall. 397. Gupta, P.; Chaudhary, R. S.; Prakash, B. Br. Corr. J.
1969, 17, 1311. 1983, 18, 98.
367. Sanderson, M. D.; Scully, J. C. Corr. Sci. 1970, 10, 165. 398. Walker, R. Corrosion 1973, 20, 290.
368. Dunwald, H.; Wagner, C. Z. Phys. Chem. 1933, 22, 212. 399. Lewis, G. Br. Corr. J. 1981, 16, 169.
369. Wagner, C. Z. Phys. Chem. 1933, 21, 25. 400. Subramanyan, N. C.; Sheshadri, B. S.; Mayanna, S. M.
370. Wagner, C. Pittsburgh International Conference on Br. Corr. J. 1984, 19(4), 177.
Surface Reactions; Corrosion Publishing: Pittsburgh, 401. Badawy, W. A.; Ismail, K. M.; Fathi, A. M. Electrochim.
1948; pp 77–82. Acta 2006, 51(20), 4182.
371. Hoar, T. P.; Price, L. E. Trans. Faraday Soc. 1938, 34, 867. 402. Francis, R. The Selection of Materials for Seawater
372. Price, L. E.; Thomas, G. J. J. Inst. Med. 1938, 63, 21. Cooling Systems: A Practical Guide for Engineers; NACE:
373. Schu¨ckher, F.; Lampe, V. Prog. Met. 1965, 105, 192. Houston, 2003.
374. Wood, G. C.; Chattopadhyay, B. J. Inst. Met. 1970, 403. Avery, S. V.; Howlett, N. G.; Radice, S. Appl. Environ.
98, 117. Microbiol. 1996, 62(11), 3960.
375. Whittle, D. P.; Wood, G. C. J. Inst. Met. 1968, 96, 115, 404. Kim, J. H.; Cho, H.; Ryu, S. E.; Choi, M. U. Arch.
J. Corr. Sci. 1968, 8, 295. Biochem. Biophys. 2000, 382(1), 72.
376. Swaroop, B.; Wagner, J. B., Jr. J. Electrochem. Soc. 405. Karlstrom, A. R.; Levine, R. L. Proc. Natl. Acad. Sci. USA
1967, 114, 685. 1991, 88(13), 5552.
377. Ashby, M. F.; Smith, G. C. J. Inst. Met. 1963, 91, 182. 406. Pena, M. M.; Lee, J.; Thiele, D. J. J. Nutr. 1999, 129(7),
378. Bolsaitis, P.; Kahlweit, M. Acta Metall. 1967, 15, 765. 1251.
379. Pötschke, J.; Mathew, P. M.; Frohberg, M. G. Z. 407. Noyce, J. O.; Michels, H.; Keevil, C. W. J. Hosp. Infect.
Metallkunde 1970, 61, 152. 2006, 63, 289.
380. Alloy 400 for use in High Pressure Feedwater Heaters; 408. Noyce, J. O.; Michels, H.; Keevil, C. W. Appl. Environ.
Nickel Institute Publication 14021, Nickel Institute: Microbiol. 2006, 72, 4239.
Alvechurch, UK, 1993. 409. Noyce, J. O.; Michels, H.; Keevil, C. W. Appl. Environ.
381. Moore, C.; Bindley, D. Proceedings of the Second Microbiol. 2007, 73, 2748.
International Congress on Metal Corrosion, New York, 410. Casey, A. L.; Lambert, P. A.; Miruszenko, L.; Elliot, T. S. J.
1963; NACE: Houston, 1966; p 391. Copper for preventing microbial environmental
382. Castle, J. E.; Harrison, J. T.; Masterson, H. C. contamination; Interscience Conference on Antimicrobial
Proceedings of the Second International Congress on Agents and Chemotherapy (ICAAC) ASM, Washington,
Metal Corrosion, New York (1963) NACE: Houston, 1966; 2008.
p 822. 411. Casey, A. L.; Adams, D.; Karpanen, T. J.; Lambert, P. A.;
383. Hopkinson, B. E. ASME 1962, Paper No. 62-WA. Cookson, B. D.; Nightingale, P.; Miruszenko, L.;
384. Wiedersum, G. C.; Tice, E. A. ASME WA/CT-3, ASME, Shillam, R.; Christian, P.; Elliott, T. S. J. The role of
1964, Paper No.64. copper in the reduction of contamination of the hospital
385. Castle, J. E.; Harrison, J. T.; Masterson, H. G. Br. Corros. J. environment, submitted to J. Hospital Infection, March
1966, 1, 143. 2009.
386. Otsu, T.; Sato, S. Trans. Jpn. Inst. Met. 1961, 2, 153. 412. Mawella, J. UK Ministry of Defence, Abbey Wood,
387. Sato, S. Sumitomo Light Metal Tech. Rep. 1964, 5(1), 2; Bristol, Communication on Corrosion performance of
1964, 5(2), 27; 1964, 5(3), 231; 1964, 5(4), 290. NES 824 copper-nickel chrome www.
388. Brush, E. G.; Pearl, W. L. Corrosion 1969, 25, 99. marinecorrosionforum.org, 2005.
389. Tromans, D.; Sun, R. J. Electrochem. Soc. 1991, 138(11), 413. Hurtado, M. R. F.; Sumodjo, P. T. A.; Benedetti, A. V.
3235–3244. J. Electrochem. Soc. 1993, 140(6), 1567–1571.