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Crundwell 2010
Crundwell 2010
19 Sacrificial Anodes
R. F. Crundwell
Chartley Consultants, Foar Oaks, Sutton Coldfield B74 4TH, UK
2763
2764 Electrochemical Protection
Table 1 Anode potentials of various alloys used in parameter against which the anode cost per unit
cathodic protection anode weight should be evaluated.
Alloy Anode potential Max anode The anode efficiency is the percentage of the the-
(V vs Ag/AgCl/ capacity (A h kg1) oretical anode capacity that is achieved in practice:
Seawater)
Anode capacity
Anode efficiency ¼ 100%
Al–Zn–Hg 1.0 to –1.05 2830 Theoretical capacity
Al–Zn–Sn 1.0 to 1.05 2600 (heat treated)
Al–Zn–In 1.05 to 1.15 2700 Anode efficiency is of little practical significance and
Zn–Al–Cd 1.05 780 can be misleading. For example, magnesium alloy
Mg–Mn 1.70 1230 anodes often appear to have an efficiency of around
Mg–Al–Zn 1.50 1100–1230 50%, while for zinc alloys, the value exceeds 90%; it
does not follow that zinc alloy anodes are superior to
those based on magnesium. Efficiency will be encoun-
will cease. Different materials have different poten-
tered in many texts on sacrificial anode cathodic
tials (Table 1). Occasionally, a less negative potential
protection.
will be specified because some degree of corrosion is
permissible. It should be noted that in a mixed metal
system, the protection potential for the most base
4.19.2.3 Anode Requirements
metal is adopted although the designer should take
into account any deleterious effect that over protec- The fundamental requirements of a sacrificial anode
tion may have on the nobler component and the need are to impart sufficient cathodic protection to a struc-
to supply excessive current if it is an efficient cathode. ture economically and predictably over a defined
The cathodic protection of mixed metal systems can period, and to eliminate, or reduce to an acceptable
be a complex subject and is discussed in detail later in level, corrosion that would otherwise take place.
the chapter. In view of the above criteria, the following proper-
The driving voltage is the difference between the ties are prerequisites for the viability of a sacrificial
anode operating potential and the potential of the anode4,5
polarized structure to which it is connected. For
1. The material must have a potential more nega-
design purposes, the driving voltage is taken as the
tive than the potential at which corrosion ceases
difference between the anode open circuit potential
on the material being protected (i.e., the anode
(unless there are data on how the anode material will
must exhibit a driving potential relative to the pro-
actually behave) and the required protection poten-
tected cathode). Thus, for steel, which is considered
tial of the structure.
protected at potentials more negative than 0.8 V
negative to the silver chloride seawater reference
4.19.2.2 Anode Capacity and Anode
electrode, the driving voltage must be capable of
Efficiency
overcoming the ohmic resistances of the anode
The anode capacity is the total coulombic charge cathode and the electrolyte in order to make the
(current time) produced by the unit mass of an anode deliver the protection current. In practice this
anode as a result of electrochemical dissolution. It is means a driving potential of at least 0.2 V more
normally expressed in ampere hours per kilogram negative than the metal to be protected.
(A h kg1); however, the inverse of anode capacity, 2. The driving potential of the anode must be stable
that is, the consumption rate (kg A1 year1), is also with respect to time and must be predictably
sometimes used. affected by the passage of current, that is, the
The theoretical anode capacity can be calculated anode material must have known and have accept-
according to Faraday’s law. From this, it can be shown able polarization characteristics.
that 1 kg of aluminum should provide 2981 Ah of 3. The anode material must have adequate capacity;
charge. In practice, the realizable capacity of the that is, it must deliver an adequate and predict-
anode is less than the theoretical value. The signifi- able number of ampere hours for every kilogram
cance of the actual (as opposed to the theoretical) consumed.
anode capacity is that it is a measure of the amount of 4. The alloy must be capable of being formed by
cathodic current an anode can give. Since anode simple and economical processes into shapes in
capacity varies among anode materials, it is the which it may be used, and it must have adequate
2766 Electrochemical Protection
mechanical strength to remain in the desired form very negative operating potentials and are therefore
throughout its designed life. able to provide a large driving voltage for cathodic
5. The alloy must be commercially viable; that is, it protection; zinc and aluminum alloys are more modest
must be capable of being produced in significant in this respect. Aluminum alloys, by contrast, provide a
quantities (the world production of sacrificial substantial current capacity which is more than twice
anodes runs into many tens of thousands of tons that available from the zinc and magnesium alloys.
per annum) and sold at a price that is acceptable to It might appear that this implies that if the driving
the users. voltage is the most important feature in a given
cathodic protection system (e.g., when there is a need
for short-term high currents or a high resistivity to
4.19.3 Sacrificial Anode Materials overcome), then magnesium alloys are to be preferred,
but if a high capacity is required (e.g., steady delivery of
While cathodic protection can be used to protect current over a long life), aluminum alloys would be
most metals from aqueous corrosion, it is most com- better. In practice, selection is significantly more com-
monly applied to carbon steel in natural environments plicated, and the topic is discussed in more detail in
(waters, soils, and sands). In a cathodic protection sys- later sections.
tem, the sacrificial anode must be more electronegative Even within a generic type of alloy, there are
than the structure. There is, therefore, a limited range significant performance differences. Thus, for exam-
of suitable materials available to protect carbon steel. ple, Al–Zn–In alloys provide a higher driving voltage
The range is further restricted by the fact that the but a lower current capacity than Al–Zn–Hg alloys.
most electronegative metals (Li, Na, and K) corrode Once a decision to use a generic type of alloy has been
extremely rapidly in aqueous environments. Thus, made, these apparently small differences in perfor-
only alloys based on magnesium, aluminum, and zinc mance may become important in the final selection.
are viable possibilities. These metals form the basis of Alloying additions are made to improve the per-
the three generic types of sacrificial anodes. formance of an anode material.5 Of equal importance
In practice, with one minor exception (pure zinc), is the control of the levels of impurity in the final
the commercially pure metals are unsuitable as sac- anode, since impurities (notably iron and copper) can
rificial anode materials. This is because they fail to seriously adversely affect anode performance. Care-
meet one or more of the prerequisites outlined above. ful quality control of the raw materials used and the
For each basis metal, alloying elements are added to manufacturing process adopted is essential to sound
ensure more acceptable properties. anode production.
Table 2 gives a list of the more important anode An intimate knowledge of the factors influencing
materials by broad categories, and some indication of the operation of sacrificial anodes and design para-
their operating parameters. It is clear that there are meters is essential if a full appreciation of how best to
major differences in performance between one generic select an anode and achieve optimum performance is
type and another. Thus, the magnesium alloys have to be realized. The following considerations deal with
those factors, which ultimately determine anode
Table 2 Typical basis material composition require- performance.
ments for anode alloys
be desirable to tolerate a level of impurities and to with iron levels around 20 ppm means that iron is
overcome their action by making alloying additions. no longer an issue in the production of zinc anodes.
Alloying elements may also be added for other rea- The same is true for aluminum as world demand
sons, which are important to anode production and for higher purity ingot for the electronics indus-
performance. try means that aluminum with a notional purity of
In general, sacrificial anode alloy formulations are 99.85% is readily available with less than 0.08% iron
proprietary and may be covered by patents. The pat- and 99.90% with iron levels selectable at below 0.05%.
ent documents are often very imprecise when they Other heavy metal impurities (especially copper
relate to compositions that will produce effective and nickel) have similar adverse effects on all generic
anodes and quite inaccurate in ascribing the func- alloy types. In their case, sequestering has not proved
tion to a given alloying element. While the commer- successful, and control of input quality is used to
cial literature is more specific when it relates to keep their concentration acceptably low.5 It is impor-
compositions, it rarely details the purpose of an alloy- tant that these impurities are specified at the time of
ing addition. In discussing alloy composition here, the selecting a supplier as what is a deleterious impurity
treatment derives from the technical literature and to one application may be a beneficial ingredient to
is necessarily a broad-brush account. The reader is another; for example, levels of nickel in aluminum
referred to the wealth of literature published over the sourced in the Middle East were not considered rele-
past 50 years, for example, as reviewed by Googan.6 vant for most applications but resulted in significant
reduction in capacity when used for anode production.
Similarly, naturally occurring levels of gallium present
4.19.4.2 Impurities
in aluminum feedstock sourced in the United States for
One important feature of an anode alloy is that it the development of Al–Zn–Si–In alloys contributed to
should dissolve with a capacity approaching the the- the activation process, but when the alloy was licensed
oretical value. That is, all the electrons released by for production in the United Kingdom, locally sourced
the metal dissolving should be transferred to the aluminum did not have the gallium impurity, and it
structure to support the cathodic reaction there, and had to be deliberately added to achieve the desired
should not be wasted in local cathodic reactions on its properties.
own surface.
In all the generic types of sacrificial anode alloys,
4.19.4.3 Alloying Additions
the presence of iron is found to be deleterious. This is
because an intermetallic compound formed between We have seen that the adverse effect of impurities can,
it and the basis metal proves to be a good cathode. Its within limits, be controlled by alloying additions. Thus,
presence-c will result in a substantial lowering of the silicon and aluminum are added to zinc and manganese
capacity of an anode. Moreover, the presence of this to magnesium, to counter the effect of iron.
cathodic material will often raise (make less negative) Additions are made for other purposes, all of
the anode operating potential and may, in the limit, which aim to improve the performance of the anode.
promote actual passivation. Thus, the driving force These include lowering the anode operating potential
available from the anode is reduced or completely to increase the driving voltage, avoiding passivation,
destroyed. For example, when the solid solubility of increasing the anode capacity, improving the dissolu-
iron in zinc (14 ppm) is exceeded, the anode oper- tion morphology, modifying the mechanical properties
ating potential becomes more positive. This has been of the dissolution product to promote detachment, and
attributed to the formation of Zn(OH)2 around inter- improving the mechanical properties of the anode.
metallic precipitates of FeZn13.7 The presence of Table 3 lists some common zinc anode alloys.
iron has a similar adverse effect in aluminum8 and In three cases, aluminum is added to improve the uni-
magnesium5 alloys. formity of dissolution and thereby reduce the risk of
There are two ways of avoiding the iron problem: mechanical detachment of undissolved anode material.5
to control the iron added with the basis metal or to Cadmium was traditionally added to encourage the
sequester the iron in some way to render it ineffective. formation of a soft corrosion product that readily crum-
In practice, it is not possible to permit more than a bles and falls away so that it cannot accumulate to
limited iron content because sequestering is only eco- hinder dissolution7; however, its use is now restricted
nomic and practicable within defined limits. The due to environmental concerns. The Military Specifi-
wider availability of electrolytically smelted zinc cation9 material was developed to avoid the alloy
2768 Electrochemical Protection
Alloy Component ASTM B4 18-88 ASTM B 418-88 US Mil Spec DNV Elevated temp
(wt%) Type I Type II A 18001 K
passivating as a result of the presence of iron.5 It later Table 4 Proprietary aluminum anode alloys
became apparent that this material suffered intergran-
Alloy Al–Zn–In Al–Zn–Sn Al–Zn–Hg
ular decohesion at elevated temperatures (>50 C)
Component
with the result that the material failed by fragmenta- (wt%)
tion.10 The material specified by Det Norske Veritas11
was developed to overcome the problem: the aluminum Fe 0.12 max 0.13 max 0.08 max
Si 0.05–0.20 0.11–0.21
level was reduced under the mistaken impression that it Zn 2.0–6.5 4.0–6.0 0.35–0.5
produced the problem. It has since been shown that Hg 0.035–0.050
decohesion is due to a hydrogen embrittlement mecha- In 0.01–0.02
nism,12 and that it can be overcome by the addition Sn 0.1
of small concentrations of titanium.13 It is not clear Cu 0.006 max .01 max 0.006 max
Ti 0.02 max 0.02 max 0.02 max
whether the titanium acts as a getter for hydrogen or Others 0.02 max 0.02 max 0.02 max
simply serves to refine the grains and increase the grain o/c potential 1.10 V 1.10 V 1.05 V
boundary area thereby diluting the embrittlement Ag/AgCl/
effect. It is claimed that recently developed alloys with seawater
magnesium additions are also resistant to intergranular Capacity 2700 Variable 2830
(A h kg1)
attack at elevated temperatures.5,10
Although aluminum is a base metal, it spontane-
ously forms a highly protective oxide film in most
aqueous environments; that is, it passivates. Conse- Mercury has become associated with environmental
quently, it has a relatively noble corrosion potential issues and is now seldom used in offshore applications.
and is then unable to act as an anode to steel. Low Zinc and indium additions give a less noble operat-
level mercury, indium, or tin additions have been ing potential but are associated with a lower capac-
shown to be effective in lowering (i.e., making more ity. In practice this effect on the operating potential
negative) the potential of aluminum; they act as acti- can be quite significant. The driving voltage between
vators (depassivators). Each element has been shown to Al–Zn–Hg (open circuit/operating potential –1.05 V)
be more effective with the simultaneous addition of and steel (protection potential –0.80 V) is 0.25 V. The
zinc. Zinc additions of up to 5% lower the anode use of Al–Zn–In provides a 20% increase in the driving
operating potential, but above this level, no benefit is voltage and thereby the possibility of a higher current
gained. Below 0.9% zinc, there is little influence on the output from equal sized anodes. Thus, both alloys have
performance of aluminum anodes.5 Table 4 lists a important advantages and disadvantages.
number of the more common commercial alloy groups. The Al–Zn–Sn alloys require careful solution heat
The best capacities in seawater are obtained from treatment in their production to achieve optimum
alloys containing zinc and mercury, but this is achieved properties. Inevitably, this leads to more expense,
at the expense of a somewhat more noble operating longer production times, and a need for greater
potential. Higher zinc additions at around 5% result in quality control. The advent of the alloys containing
an alloy highly tolerant of burial in seabed muds. mercury or indium rendered these alloys very much
Sacrificial Anodes 2769
less attractive. Magnesium additions (0.1–2.0%) to aluminum, zinc, and manganese to magnesium serve
Al–Zn–In alloys have been made, but it is not to improve the anode capacity and reduce the
known whether this was a deliberate addition to operating potential, compared with that of pure mag-
improve a particular property or because the starting nesium. There is, however, no difference between the
point for alloy development was an existing structural capacity of Mg–Mn and Mg–Al–Zn anodes. Mg–Al–
alloy. These materials can harden with age and hence Zn alloys are called ‘high purity’ when produced from
suffer reduced ductility; since this can subsequently virgin magnesium to distinguish them from a series of
lead to longitudinal cracking of the anodes, they alloys developed after the Second World War when
should not be cast in thin sections or stored at elevated large amounts of magnesium alloy scrap were available.
temperatures (full sun in hot climates). Higher levels
of magnesium (up to 8%), while improving strength
4.19.4.4 Metallurgical Factors
and casting characteristics, incur the disadvantage of a
reduced capacity. In producing anodes, the production method must
Both titanium and boron can be added as grain not compromise the benefits of alloy formulation.
refiners to ensure small grain size and hence high A number of undesirable anomalies can occur during
surface area grain boundaries.14 This reduces the risk production, which may detract from the desired anode
of preferential attack at grain boundaries and promotes properties. Some of these anomalies are discussed
more uniform dissolution. This effect also results in an below. A detailed account of finished anode require-
alloy that is less susceptible to ‘hot shortness.’ ments can be found elsewhere.11,15
Typical proprietary magnesium anode materials Although most anodes are made by gravity casting,
are given in Table 5. Magnesium anodes comprise some are made by continuous or semicontinuous
two distinct types, the Mg–Mn and Mg–Al–Zn alloy casting or extrusion. The method of casting affects
systems. Addition of up to 1.5% manganese to high- the physical structure of the anode. That is, the asso-
purity magnesium yields a material with an operating ciated cooling process will influence the segregation
potential of –l.7 V versus Ag/AgCl/seawater. The or distribution of alloying constituents. In some cases,
Mg–Mn alloys therefore exhibit very high driving it is undesirable to permit segregation since this may
potential and thus find application in particularly lead to preferential attack at grain boundaries. How-
resistive environments. Mg–Al–Zn anodes have an ever, it is believed that segregation of activating ele-
operating potential (1.5 V versus Ag/AgCl/seawa- ments during cooling benefits the performance of some
ter) 200 mV above that of the Mg–Mn alloys. This is alloys. This mechanism is a suggested explanation
very favorable in view of problems with overprotec- for the mercury- and indium-rich phases round on
tion. Thus, they are more popular in typical environ- the surfaces of aluminum anodes.13 The increased
ments than the Mg–Mn alloys. The alloys also surface concentrations of these elements aid activation
contain manganese, which is added to overcome the and are therefore beneficial.
deleterious effects of iron.5 Alloying additions of Significant porosity within the anode is an indica-
tor of the presence of dissolved gasses in the molten
alloy and is an indicator of poor foundry practice and
Table 5 Proprietary magnesium anode alloys
should be a cause for rejection and further investiga-
Alloy Component Mg–Mn Mg– Al– Zn tion. The inclusion of extraneous matter, as a conse-
(wt%) (Galvomag®) (high purity) quence of unclean foundry practices, may increase
the tendency to fragmentation.
Cu 0.02 max 0.02 max
Al 0.01 max 5.3–6.7 Cracking of anodes during casting is, in some cases,
Si – 0.10 max unavoidable due to the stresses imposed by cooling
Fe 0.03 max 0.003 max particularly those occurring between the cooling con-
Mn 0.5–1.3 0.15 min tracting anode and the mould heating and expand-
Ni 0.001 max 0.002 max
ing. The problem is more common in Al–Zn–Hg
Zn – 2.5–3.5
Sn 0.01 max – anodes and less common when continuous or semi-
Pb 0.01 max – continuous casting is used. Longitudinal cracks can-
o/c potential vs. Ag/ –1.7 –1.5 not be accepted, as these will lead eventually to
AgCl/seawater mechanical loss of material. A greater tolerance to
Capacity 1230 1230
transverse cracks can be exercised although foundry
Ahrs/kg
practice and the use of grain refinement additions can
2770 Electrochemical Protection
minimize their occurrence. For example, one quality for damage to be 50 C. The material is not recom-
specification permits an anode completely supported mended above 40 C10 although special zinc based
by the insert to have transverse cracks of unlimited materials for temperatures exceeding 50 C have been
length and depth provided that there are no more than developed.11 Pure zinc, which does not suffer inter-
ten cracks per anode and their width does not exceed granular decohesion, will passivate under these con-
5 mm.15 This is somewhat arbitrary but emphasizes ditions. It is claimed that newly developed Zn–Al–Mg
the point that cracks that threaten anode integrity anodes will perform satisfactorily at elevated tempera-
are of greatest importance. tures.10 Nevertheless, Al–Zn–In anodes have been spe-
The anode material must stay firmly attached to cified for operation above 50 C.10 Furthermore, steps
the steel insert, which is necessary to conduct the are now taken to ensure that the anode design prevents
current from the anode so that the structure remains anode material being exposed to elevated temperatures
effective, throughout its design life. Consequently, under buried conditions.
surface preparation of the insert prior to casting to It must be observed that most anode testing and
ensure a sound bond with the anode material is essen- development for use at elevated temperatures both
tial. Voids at the insert–anode material interface are in laboratories and in the field has been under iso-
undesirable, as these will also affect the bond integ- thermal conditions, and it is often erroneously as-
rity. Dry blast cleaning to near white metal at the time sumed that the anode temperature is that of the
of casting is the usual preparation for aluminum alloy product, whereas the anode is probably at a signifi-
anodes,15 and coating by hot dip galvanizing or elec- cantly lower temperature but is operating under high
trogalvanizing is used for inserts of zinc or magnesium heat transfer conditions and that consideration should
anodes. Zinc coating of inserts for aluminum anodes be given to placing a thermal barrier between the
must not be used as the coating enables the molten anode and the structure to minimize both tempera-
alloy to dissolve the insert. ture and heat transfer effects.
The presence of H2S (from bacterial activity in
anaerobic saline mud, for example) can result in a
4.19.4.5 Environmental Factors
significant decrease (16%) in capacity and loss of
The conditions of environmental exposure play a operating potential for Al–Zn–In anodes.17
key role in determining anode performance. Indeed, Environmental resistivity and chloride content will
specific environments often preclude, or necessitate, affect anode performance. Aluminum alloy anodes
the use of particular anode materials. require the presence of chloride ions to prevent pas-
This section is not intended to deal with those sivation. Land-based applications generally provide
environmental factors that influence cathodic current insufficient chloride levels for this purpose. Conse-
demand (e.g., oxygen availability or the presence of quently, aluminum alloy anodes predominantly find
calcareous deposits) but those that directly affect the application in marine environments although some
performance of the anodes. water produced from oil or gas wells is both saline and
Temperature is of particular importance to the hot, and aluminum anodes find application in corrosion
performance of anodes, especially when anodes are protection in vessels handling these fluids. The capacity
buried. Anodes may often be used to protect pipelines and operating potential, of aluminum alloy anodes in
containing hot products. Thus, temperature effects particular, illustrated in Figures 1 and 2, are dependent
must be considered. Al–Zn–In anodes experience on the degree of salinity. With reducing salinity, the
greatly reduced capacity in open seawater at tempera- anode capacity will decrease and the operating poten-
tures above 70 C16 (down to 1200 A h kg1 at 100 C) tial rise. This becomes increasingly significant below
and in seabed muds in excess of 50 C16,17 (900 A h 10–20% seawater strength and is important for design
kg1 at 80 C). At elevated temperatures, passivation of in estuarine conditions. Passivation of aluminum zinc
both aluminum alloys and pure zinc can occur.18 Con- indium alloy anodes may occur as a consequence of
siderable improvement in performance (capacity, and electrolyte stagnation, particularly, if the anode is
to a lesser extent operating potential) has been claimed immersed in silt or sand; zinc and Al–Zn(5%)–Hg
for a range of modified Al–Zn–In anode materials perform reasonably under these conditions.
containing a deliberate alloying addition of silicon. The capacity of an anode is dependent on the
Zinc anodes have also experienced problems anode operating current density.16 To some extent,
at elevated temperatures in saline mud, suffering it will be governed by its environment but, in part, is
intergranular decohesion at approximately 70 C.19 within the control of the design. Certainly, wholly
Later work by the same authors showed the threshold unsuitable current densities can usually be avoided
Sacrificial Anodes 2771
860 +
Anode current density:
- 4300 mA m–2
0.90
2150 - 2150 mA m–2
- 860 mA m–2
+ - Zn-2150 mA m–2
0.80
4300
1 3 12 33 100
Log percent seawater
Figure 1 Electrochemical potential of aluminum and zinc anodes as a function of salinity and current density.
2500
Anode current density:
- 4300 mA m–2
2250
- 2150 mA m–2
- 860 mA m–2
+ – Zn- 2150 mA m–2
2000
1000
+
750 + + +
1 3 12 33 100
Log percent seawater
Figure 2 Capacity of aluminum and zinc anodes as a function of chloride ion concentration and current density.
by correctly sizing the anodes. At lower operating However, the choice is often governed by other con-
current densities, some anodes exhibit reduced capac- straints and frequently becomes a compromise.
ity; this is shown in Figure 3. Long periods of low
operating current density can lead to passivation. This
may result in failure to activate when the current 4.19.5.1 Zinc
demand increases (as can occur with anodes on coated
Of all the anode materials, zinc is arguably the most
structures when the coating deteriorates).
reliable. It has, with few exceptions, reliable electro-
chemical performance; the exceptions lie within
4.19.5 Selecting the Appropriate the area of high temperature operation. Zinc pro-
Anode Material vides the lowest driving voltage of the generic alloy
types. It is therefore unsuitable in highly resistive soils,
It is desirable to choose an anode material with the except possibly as a ribbon, and in low salinity waters.
lowest cost per ampere hour of current supplied. However, an operating potential of –1.05 V versus
2772 Electrochemical Protection
2750
2500
Current capacity-amp. (h kg–1)
2000
Laboratory data
6 mos. field data
1750 1 year field data
Ag/AgCl/seawater cannot lead to overprotection, substantial weight savings, which can be of great
which is an advantage where concerns for coating dis- importance (e.g., offshore structures wherein the
bondment and hydrogen damage of high strength steel float-out weight is of paramount importance and
(>700 MPa) exist.11 the cost of increased weight of anodes can be many
Zinc anodes have a poor capacity (780 A h kg1) times the cost of the anodes and their installation).
compared with aluminum (>2500 A h kg1) although Aluminum anodes comprise essentially three
with its much higher density equivalent life anodes are generic types: Al–Zn–In, Al–Zn–Hg, and Al–Zn–Sn.
frequently of similar dimensions. However, zinc is not Since Al–Zn–Sn alloys have largely been superseded,
susceptible to passivation in low chloride environments they will not be discussed further. Indium and mer-
or as a consequence of periods of low operating current cury are added to aluminum to act as activators, that
density. The reliable operational characteristics of zinc is, to overcome the natural passivation of aluminum.
often outweigh the apparent economic attraction of Despite this, aluminum anodes are not suitable for
aluminum, which can passivate under such conditions. low chloride environments, which would lead to pas-
At the time of writing, raw zinc costs about half the sivation. These anodes are therefore not used for
price of aluminum, which can significantly contribute land-based applications (although examples of use
to enhancing the appeal of zinc. in environments such as swamps do exist). Similarly,
Zinc anodes do not find application at tempera- their use in low chloride aqueous environments such
tures in excess of 50 C. Zn–Al–Cd alloys suffer as estuaries must be viewed with caution.
intergranular decohesion, and high purity zinc will Traditionally, the technical choice between
passivate. Zinc anodes are not predominant in Al–Zn–In and Al–Zn–Hg anodes is influenced by
onshore or offshore applications, but they find use their respective operating potentials and capacities;
under both conditions. The use of zinc anodes on however, more recently the environmental concerns
fixed structures in the North Sea is now proscribed have restricted the use of mercury-containing anodes.
under EU regulation (Paris Convention). Where an additional driving voltage is required (such
as in seabed mud), Al–Zn–In anodes may be preferred
to ensure adequate structure polarization. Alterna-
4.19.5.2 Aluminum
tively, a lower driving potential may be acceptable
The great attraction of aluminum anodes is their very where the additional capacity (and hence weight sav-
high capacity, over three times that of zinc. They are ing) is the predominant factor; this favors Al–Zn–Hg
attractive from a cost point of view and also offer anodes.
Sacrificial Anodes 2773
Aluminum anodes are less constant in their elec- 1. Screening tests enable the rapid selection of mate-
trochemical characteristics than zinc. This presents rials that show potential as candidates for the given
no major problem provided the designer is aware of application. These tests may typically use a single
their properties. They suffer from reduced capacity parameter (e.g., operating potential at a defined
and increased operating potential (and hence risk of constant current density) as a pass/fail criterion
passivation) with increasing temperatures above and are normally of a short duration (usually hours)
approximately 50 C, decreasing salinity (Figure 2) with test specimen weights of the order of a few tens
and decreasing operating current density (Figure 3). or hundreds of grams. The tests are not intended to
Aluminum alloys are susceptible to thermite spark- simulate field conditions precisely and often include
ing when dropped on to rusty surfaces. Consequently, cutting samples from larger castings and surface
their use may be subject to restrictions. For example, preparation to give uniformity/across tests.
in ships’ tanks where explosive gases or mixtures of 2. Performance testing is long term (months to years).
gases can accumulate, the weight of the anode and Once a potentially attractive formulation has been
the height at which it is suspended are strictly con- identified, it is usual to produce detailed data on
trolled. This is because thermite sparking is dependent its performance and behavior as an anode material
on the kinetic energy of the anode released on impact, under the anticipated exposure conditions. For this
should it fall. reason, the test should mirror as closely as possible
the expected operating conditions, or where prac-
ticable be conducted in the field. Large specimens
4.19.5.3 Magnesium
(tens or hundreds of kilograms) in the as cast con-
Magnesium anodes are of two generic types, Mg–Mn dition would be used for these tests.
and Mg–Al–Zn. Both alloy systems have a high driving 3. Quality control tests are intended to detect pro-
voltage and therefore find application in high resistiv- duced materials that deviate from manufacturing
ity environments: soils and fresh, or brackish waters, for specifications, and thus may result in questionable
example. The Mg–Mn alloy is useful in particularly performance. This area of anode testing has prob-
resistive environments (up to 6000 O cm) as a result ably been the subject of more debate and contro-
of an available driving voltage 200 mV greater than versy than any other. The anode alloy is usually
Mg–Al–Zn anode. Because magnesium is nontoxic, subjected to chemical analysis usually by spark emis-
its use is permissible in potable water systems wherein sion spectroscopy, which is the primary quality con-
the conductivity is low. trol check. The preparation of samples for this
The high driving voltage may, however, result in testing, especially if small samples from the melt
overprotection. Combined with relatively poor capacity or samples that are cut from a full anode are to
(1230 A h kg1) and high unit cost, these disadvantages be used, must be validated to ensure that analysis
mean that magnesium rarely finds application in subsea is not corrupted by surface preparation. The risk
environments where alternatives are available. Despite is reduced if the analytical technique uses dissolution
this, Mg–Al–Zn anodes have been used in seabed mud of the sample when surface preparation is irrelevant.
and for rapid polarization of structures (in ribbon form). 4. Exposure testing has generated a whole industry of
The susceptibility of magnesium to thermite spark- quite dubious value to the final product. It was first
ing when dropped onto rusty surfaces precludes its developed to act as a quality check on the efficacy
consideration for applications involving a spark hazard, of solution heat treatment of Al–Zn–Sn alloy
for example, tankers carrying inflammable petroleum anodes when a simple capacity test based on mea-
products. surement of hydrogen evolved under impressed
current was used as a go or no-go acceptance test.
Samples, heat treated alongside full sized anodes,
4.19.6 Anode Testing were tested overnight. Unfortunately, the results
were expressed in the same units as anode capacity,
Tests or sacrificial anode materials are generally con- and electrochemical testing has now been man-
ducted for three reasons: for screening (or ranking), dated to do a job that was never intended, that is,
performance information, and quality control. The to confirm the actual long-term performance of full
application of sacrificial anodes for the protection of sized anodes in service. The use of short-duration
structures requires the development of suitable (hours or days) tests on small samples, which have
anode materials for the exposure environment. had some form of surface treatment not typical of
2774 Electrochemical Protection
full-sized anodes, in which the test conditions to be protected, which is restricted to uncoated areas
attempt to reflect the environment of operation, and holidays in the coating. It is therefore good
for example, using artificial seawater for a marine practice to assume an arbitrary level of coating break-
application, cannot and never will reflect full-scale down for coated areas to obtain the area of metal
operation. In more than 30 years of experience, this requiring cathodic protection. During installation of
author has not heard of a single instance in which a larger diameter subsea pipelines (>8 in. dia), pipe
sensible sized anode (>10 kg) made from a correctly sections are prepared in 40 ft lengths onshore where
formulated alloy has failed to deliver electrochemi- coating integrity can be rigorously controlled; however,
cal performance as expected. Conversely, the exam- field joints are often made under severe constraints as
ples of small-scale tests on samples giving erratic the pipe is prepared to go over the stinger. It is there-
results are legion, and the subsequent contractual fore often assumed that these field joints will fail, and
and so called scientific wrangles have contributed 2.5% coating loss is used as the basis for design
nothing to corrosion control. Presented area % breakdown
Area to be protected ¼
100
4.19.7 Cathodic Protection System Breakdown will vary through the life of a structure
Design with the result that the area requiring protection will
change. Various estimates of coating breakdown have
4.19.7.1 Design Parameters
been made, and Table 6 provides an example based on
Before a satisfactory cathodic protection system using a single coat epoxy coating system on blast cleaned
sacrificial anodes can be designed, the following infor- steel exposed to seawater, for example, a subsea com-
mation has to be available or decided upon: pletion structure. Table 6 reasonably assumes a rate of
1. the area of the steelwork to be protected; breakdown that varies with time; this will be much
2. the type of coating, if any, that is to be used; greater for fully exposed surfaces compared, for exam-
3. the cathodic current density; ple, to pipeline coatings which may be overlaid with
4. cathodic protection system life. several centimeters of reinforced concrete which are
then trenched into the seabed, as are shown alongside.
While the data given here is general guidance for A ships hull may be expected to lose 10–20% or even
many situations, detailed guidance will be given in more of its coating system in a relatively short period
classification society or client rules, and these will dependant on operating location. The significance of
take precedence and may change based on the expe- the area of steelwork is that the greater the area, the
rience gained in actual operation. greater the weight and/or the area of anode material
required for protection.
4.19.8 Area of Steel Requiring
Protection and Coating 4.19.9 Cathodic Current Densities
Considerations for Protecting Steel
The area of bare steel to be protected is usually calcu- Examples of current density requirements for the pro-
lated from drawings and knowledge of the actual struc- tection of steel (to achieve a steel potential of –0.8 V
ture and must account for all electrically continuous
steelwork exposed to the electrolyte. Steelwork not Table 6 Guidance on coating breakdown for offshore
structures
specified in drawings and subsequently overlooked is
a common cause of underdesign. In one classic exam- Steel structures fully exposed simple epoxy coating
ple, the current drain to the conductors of an offshore
Lifetime (years) Coating breakdown %
production platform was ignored with near disastrous Initial Mean Final
consequences and a requirement for a gigantic retrofit 10 2 7 10
program. In practice, the area is usually taken assuming 20 2 15 30
the steel surfaces to be flat without corrugations, inden- 30 2 25 60
tations, or surface roughness. An allowance for uncer- 40 2 40 90
tainties in real area is normally involved. Pipeline with glass fiber/bitumen and 70-mm reinforced
concrete weight coat
Many structures, especially pipelines, are coated. 40 1 2.5 5
Thus, the presented area far exceeds the area of steel
Sacrificial Anodes 2775
Table 7 Guidance on current density for cathodic pro- where W is the total mass of anode material (kg); A,
tection of bare steel the structure area to be protected (m2); iav, the mean
Location Current density structure current density demand (A m1); l, the
(mA m2) design life in years (1 year ¼ 8760 h); and C is the
anode capacity (A h kg1).
Initial Mean Final
Obviously, the total weight of the anode material
Northern North Sea 180 90 120
Southern North Sea 150 90 100 must be equal to or be greater than the total weight, W,
Arabian Gulf 130 70 90 calculated above. Similarly, each anode must be of suffi-
Indian Ocean 130 70 90 cient size to supply current for the design life of the
Australia 130 70 90 cathodic protection system. The anodes must also
Brazil 130 70 90
deliver sufficient current to meet the requirements of
West Africa 130 70 90
Gulf of Mexico 110 60 80 the structure at the beginning and end of the system’s life.
Indonesia 110 60 80 That is, if current demand increases (as a result of coating
Saline mud 25 20 15 breakdown, for example), the output from the anodes
should meet the current demands of the structure.
versus Ag/AgCl/seawater) are given in Tables 7. It
should be realized that the current demand of a struc- 4.19.10.2 Anode Size and Shape
ture will be influenced by, inter alia, temperature, degree In practice, while there is often an extensive range of
of aeration, flow rate, protective scales, burial status, suitable anode sizes to select from, economics may
presence of bacteria, and salinity. dictate a bespoke anode for a project depending on
It is important that the correct current density its precise requirements. Computer programs are
requirement is assigned for design purposes. If too used to optimize (minimize) the number of anodes
high a value is used the structure may be overpro- required to satisfy the often conflicting protection
tected and anode capacity wasted. On the other hand, requirements. The cost of the anode insert in a plat-
if too small a value is used it will mean that the form anode may be close to that of the anodic material,
protection system will not achieve its design life. and the cost of lifting, welding, etc. is substantially
more than that of the anode. Furthermore, after a set
4.19.10 System Life of moulds has been used to produce several thousand
anodes, they will probably only be fit for recycling.
Cathodic protection systems may be designed with a The current output from an anode will depend on
life as short as 1 year or more than 40 years. The its resistance, which will be a direct function of shape
greater the time of protection, the greater the mass and size. Generally, larger anodes will have a higher
or anode material that is required. current output. Anodes of the same weight but dif-
Intermittent exposure and local conditions need fering shape can have different outputs because the
to be considered also. The ballast or storage tanks surface area to weight ratio will not be equal for all
of ships will experience periods of complete sub- possible dimensions. Thus, for a given weight of
mergence and partial coverage, and may at times be anode, the shape will offer a degree of flexibility
empty. Similarly, the wetted areas of offshore struc- when considering current output.
tures may be governed by tidal and seasonal variations.
Local requirements must therefore be considered in 4.19.10.3 Anode Output
order to achieve the optimum amount of anodic mate- Anode output is the current available from the anode
rial to achieve the life of the system. under the design conditions. It will depend on the
shape of the anode, the resistivity of the environment,
4.19.10.1 Calculating the Weight and the protection potential of the structure, and the
Number of Individual Anodes anode operating potential. It is defined as:
Firstly, the total weight of anode required to protect ½E2 E1
the structure for its projected life is calculated. This is I ¼
R
given by:
I is the anode output (A); E1, the operating potential
iav Al 8760 of the anode (V); E2, the protection potential (V); and
W ¼
C R is the anode resistance (O).
2776 Electrochemical Protection
The protection potential of steel in aerobic environ- known. However, field data are preferable, and, in the
ments is taken as –0.80 V (versus Ag/AgCl/seawater). case of soils that can have widely varying resistivities,
they are essential.
4.19.10.4 Anode Resistance
Table 8 lists some of those formulae suitable for the 4.19.10.5 Anode Life
calculation of anode resistance, R, under submerged Having calculated the resistance, and hence the cur-
conditions. Some are based on earth resistance effects rent output, the anode life, L, is checked by the
and modifications of the formulae used in the design calculation:
of electrical earthing systems, while others are purely
empirical. Similar formulae exist for anodes in buried MU
L¼
conditions. These have been extensively researched IE
and reviewed.20–24 where L is the effective life of anode (years); M, the
To calculate the anode resistance, a knowledge of mass of single anode (kg); U, the utilization factor, for
the environmental resistivity is required. For sub- example, 0.75–0.80 for bracelet anodes and 0.95 for
merged anodes, the water resistivity can be obtained platform anodes; E, the consumption rate of the
from graphical representations such as in Figure 4, anode (kg A1 year1) (inverse of capacity in suitable
provided that the temperature and water density are units); and I is the anode output (A).
r
r 2 r 2
Short slender stand-off a,b L < 4r Ra ¼ 2pL ln 2L
r 1 þ 1 þ 2L þ 2L
r
1 þ 2L
Long flush-mountedb
r
L 4 width and L > 4 thickness Ra ¼ 2S
Short flush-mounted, bracelet and other types pffiffiffi
Ra ¼ 0:315r
A
a
The equation is valid for anodes with minimum distance 0.30 m from protection object. For anode-to-object distance minimum 0.15 m the
same equation may be applied with a correction factor 1.3.
b
For noncylindrical anodes: r = c/2p where c(m) is the anode cross-sectional periphery.
Source: DnV RP B401 (2005) – Recommended practise for cathodic protection design.
Density
30 (g l–1)
25 1000
Temperature (⬚C)
20
15
10
–5
10 20 30 40 50 60 70 80 90 100 110 120 130
Resistivity (W cm)
Figure 4 Resistivity as a function of specific gravity for seawater/fresh water mixtures.
Sacrificial Anodes 2777
U is purely a function of anode geometry and is the the anode alloy, the mould and insert will continue
fraction of anode material consumed when the remain- to expand as the anode solidifies and contracts, and
ing anode material cannot deliver the current required transverse cracking of the anode becomes more prob-
or the anode can no longer be supported by its insert. able. Grain refinement increases the high strength of
Excessive anode life is of no benefit. If the calcu- the alloy, but there are limits to how much can be
lated life is unsuitable a different anode size and/or done. Typically, a maximum anode length of 3 m and a
shape should be considered. However, this may not maximum weight of 500 kg have been imposed as
always be possible, especially for short-life, coated practical limitations. Bracelet anodes for submarine
structures, when dimensional constraints on the anodes pipelines are often sized to match a weight coating
may be imposed. thickness where there is no weight coating. The thin-
ner the anode, the lesser the impact as it goes over the
stinger during laying. Many of the same limitations
4.19.10.6 Number of Anodes that applied to platform anodes also apply to bracelets
The total number of anodes, N, is calculated from: although thin wall moulds and water cooling have
assisted reducing anode thickness where necessary.
Aiay Bracelet diameters are governed by pipe diameters
N¼
I and thickness by laying or coating considerations, but
This calculation should yield a practicable number of they are unlikely to be viable at more than 1.5 m long
anodes; that is, 10 or 10 000 anodes are both clearly and 400 kg in weight. Needless to say, some readers will
unacceptable for the distribution of protection. On an be able to quote examples of anodes larger than those
offshore oil production platform, N M must be implied here, but they will be few and far between and
equal to, or greater than, the total weight or anode almost certainly associated with some special circum-
material, W, required. stance; for example, a very large platform anode
It is also useful at this point to consider the limita- mounted on a sea bed sled or a bracelet designed to be
tions imposed by the production processes and the mounted on a large pipe to be retrofitted to a platform
actual application of the anode. For a platform anode, to compensate for a shortfall in the original design.
hypothetically, the anode could be almost as long as It can be difficult to achieve both the exact current
the water depth, but first such an anode would have output and precise weight of anode material simulta-
such a large mass and consequently inertia that it neously although, as mentioned previously, the use of
would be unlikely to survive the installation or piling iterative calculation by a computer program can opti-
processes and would be torn off. Using a stronger mize this. Where a compromise is necessary, both
insert and attachment configuration would result in must at least match design requirements.
such a large diameter core relative to the body cross A check to ensure that the anodes will deliver suffi-
section that the anode material could reasonably be cient current to protect the structure at the end of the
expected to split longitudinally during the solidifica- design life should be conducted. This entails calculat-
tion and subsequent cooling. Some of these could be ing the expected anode output at the end of its life and
overcome by semicontinuous casting rather than hor- checking that it meets the demands of the structure.
izontal gravity casting. However, this process, origi- Generally, the output is calculated using a modified
nally developed for production of extrusion ingots resistance based on an anode that is 90% consumed.
still, has the limitation of the depth of the pit into
which the casting is discharged and the lifting equip-
4.19.10.7 Anode (End Current) Distribution
ment servicing it. In order to minimize the likelihood
of some or all of these, for all practical purposes, It is evident that a greater number of anodes dis-
the maximum core diameter of a platform anode is tributed over the structure will improve current distri-
150 mm, and for this to be cast into an anode, the bution. However, aside from the unacceptable cost
cross section would have to give at least 100-mm incurred by attaching excessive numbers of anodes,
depth of cover of the anodic material over the insert. an anode must continue to function throughout the
While some foundries design a small cross-section life of the structure and must, therefore, be of sufficient
taper over the length of the anodes, others use very size to meet the design life. A very large number of
heavy preheated wall moulds and inserts (or both) heavy anodes is clearly impracticable and uneconomic.
to minimize anode mould interaction. Unless the It is essential to ensure adequate current distribu-
mould/insert is heated to the casting temperature of tion such that all of the exposed structure remains
2778 Electrochemical Protection
Moreover, the attack is preferential towards the ends and the package expands to fill the hole in the soil
of the anode such the overall appearance approxi- and eliminate voids.
mates to a traditional ‘cigar’ shape while it remains For use in high resistivity soils, the most common
supported by the insert. Anodes with a stand-off at mixture is 75% gypsum, 20% bentonite, and 5%
least 300 mm from the structure being protected in sodium sulfate. This has a resistivity of approximately
open seawater are unlikely to be seriously affected 50 ohm cm when saturated with moisture. It is impor-
by proximity and corrode nonuniformly. Anodes tant to realize that carbonaceous backfills are relevant
installed close to the structure should have an inert to impressed current anode systems and must not be
nonconducting coating (coal tar epoxy) on the face used with sacrificial anodes. A carbonaceous backfill
closest to the structure to minimize preferential is an electronic conductor and noble to both sacrifi-
attack on the close face and the possibility of anode cial anodes and steel. A galvanic cell would therefore
corrosion products building up behind the anode and be created causing enhanced dissolution of the anode,
forcing it off. This is of particular importance for and eventually corrosion of the structure.
bracelet or hull anodes and much less so for platform
anodes.
For pipeline or hull anodes, the distance through
4.19.11 Other Considerations
the anode that the insert is placed directly influences
the utilization factor since; if, for example, the insert 4.19.11.1 Calcareous Scale
is in the centre of the anode mass, the utilization
A consequence of cathodic protection in seawater is
factor will be 0.5 or 50%; if it were on the front face,
the formation of a protective calcareous scale.29 The
the U/F would theoretically be zero and on the back
increased local pH at the steel surface caused by
face, 1.0, although none of these would be practical.
hydroxyl production (a product of the cathodic reac-
Thus, if the insert is 75% of the depth of the anode
tion) favors the deposition of a mixed scale of CaCO3
from the front face, then the utilization factor is likely
and Mg(OH)2. This scale is beneficial since it is
to approximate to 75%. Ingenious designs of insert
protective and nonconducting, thus reducing the
involving a backing plate with a mesh embedded in
cathodic current density. Ensuring a high current
the back face of the anode material in order to
density in the early period of operation will encour-
approach a U/F of 1.0 have been patented but are not
age calcareous scale deposition and thus reduce the
in common use.
current requirements in the long term.
The build-up of calcareous deposits is a complex
4.19.10.10 Backfills for Anodes topic. Very high current densities will not necessarily
result in the most protective scale. In the extreme,
When zinc or magnesium anodes are used for cathodic
hydrogen evolution may rupture the scale resulting
protection onshore,25–28 they are usually surrounded
in reduced protection. An optimum current density
by a backfill, which decreases the electrical resistance
will exist, and this should be recognized.
of the anode. Small anodes are usually surrounded with
backfill in bags and large anodes are usually sur-
rounded with a loose backfill during installation. The
4.19.11.2 Combined Alloy Anodes for
backfill prevents the anode coming into contact with
Rapid Structure Polarization
the soil and suffering local corrosion, thus reducing the
capacity. By surrounding the anodes with a backfill, the Combined (or binary) alloy sacrificial anodes have
combination of the anode with soil salts is reduced, and been developed.30 An aluminum anode, for example,
this helps prevent the formation of passive films on the might have attached to it a short-life supplementary
anode surface. magnesium anode, or anodes, for quick polarization
The effect of the backfill is to lower the circuit of the structure. The overall reduction in structure
resistance and thus reduce potential loss due to the current requirements is claimed to result in an anode
environment. The additive resistances of the anode/ weight saving of 35–50%. This derives from the
backfill and backfill/soil are lower than the single increased current output from the anode early in its
anode/soil resistance. Backfills attract soil moisture operating life, giving rise to a relatively protective
and reduce the resistivity in the area immediately calcareous scale, which then reduces the current
round the anode. Dry backfill expands on wetting, demand for protection later in life.
2780 Electrochemical Protection