Marine Cathodic Protection -

Historical Trends and Recent Accomplishments

W. H. Hartt
Center for Marine Materials
Florida Atlantic University - Sea Tech Campus
101 North Beach Road
Dania Beach, Florida 33004

Abstract
Historical hallmark accomplishments pertaining to
design and fimction of cathodic protection (cp) systems for
marine structures are listed and briefly discussed. The
newly developed first-principles based slope parameter
method and a unified design equation developed therefrom
are described and compared to present standard design
practice. Application, including advantages and
limitations, of this approach to both galvanic and impressed
current cp systems upon space frame (oil production
platforms, for example), two dimensional (ship hulls), and
one dimensional (pipelines and cables) structures is
described. It is demonstrated that this method is
advantageous compared to that of existing standard
recommended practices.
I. History and Background
Technologies by which corrosion, including marine
corrosion, can be controlled or prevented include 1) proper
materials selection, 2) proper design, 3) coatings, 4)
inhibitors (not applicable, of course, for open sea water
exposures), 5) modified operating conditions, and 6)
cathodic protection (cp). The last of these (cp) was first
conceived and studied some 160-plus years ago, as reported
by the classic papers of Davy [ 1-31, and remains today the
primary corrosion mitigation technology for the submerged
portion of marine structures.
Because of its relatively high strength, good
fabricability, and low cost, steel has, for the past century,
been the most utilized material of construction for marine
structures such as ships and petroleum production
platforms. However, corrosion of steel in most submerged
sea water service proceeds at an unacceptably high rate
unless protective measures are taken. Of the different
corrosion control options mentioned above, cathodic
protection is now generally recognized as the most cost
effective and reliable for marine structures. Hallmark
accomplishments in the evolution of cp are summarized in
Table 1. Particularly noteworthy are developments of the
past two decades, which include 1) development of
improved materials for impressed current anodes, 2)
recognition of the benefits of rapid polaization, and 3)
development of a unified design equation. However, there
presently exists a relatively wide gap between the forefront
state of knowledge regarding cp and integration of
principles thereof into marine engineering practice. As an
example, the corrosion control system for many ships is
based upon an impressed current cp system that consists of
only a few anodes with control being affected via a single
reference electrode. Experiments and analyses have
indicated that the resulting hull potential and, hence, the
level of protection can vary widely depending upon
location and operating conditions [ 5 ] .

Time Accomplishments

1820's Classical experiments of Davy and introduction of cp.

1940's - 1950's I Experimental . - bv Canadian and U.S. Navies -r41._
programs
1 .
1960's - 1970's IDevelopment of improved galvanic
- anodes (aluminum base in particular). 1
Introduction of Mixed Metal Oxide (MMO) impressed current anodes. 1
Incorporation of Rapid Polarization into design practice. I
Research studies on calcareous deposits.
Development of Boundary Element Modeling methods.
Development of a first principles based unified design equation.
1990's Development of improved potential attenuation models. I

1787
 Subsequent to the advancements that transpired 50
years ago [4], cathodic protection was utilized upon
offshore petroleum production structures. The initial
systems on these structures were minimally engineered and
were successful largely because of over-design. However,
marine cp technology has become more advanced and
refined during the course of the ensuing decades largely as
a consequence of the transition from relatively shallow to
deep water where reliability is a must and a premium is
paid for over-design. Standard recommended practices are
now available that address cp design [6,7]; however, in
view of recent accomplishments (Table l), it is likely that
the next version of these will reflect significant revision.
A fundamental aspect of cp for any application is the
criterion for projecting if the level of cathodic protection is
adequate. Several of these are available; however, a
requirement of polarization to at least -0.80 VAdAgl has
evolved as prevalent for steel in sea water. It is generally
accepted that such a potential criterion for protection
corresponds to polarization of cathodic sites to the
reversible value for the anodic reaction; and theoretical
considerations, subject to certain assumptions, have shown
this to be approximately the case [SI.
11. Present Design Practice
The recommended practices addressing design of
marine galvanic anode cathodic protection systems [6,7],
which for reliability concerns are generally preferred to
impressed current ones for petroleum production structures
and pipelines, are based upon determination of the current
output per anode, I,, as calculated from Ohm’s law
according to the expression
where
4, = closed circuit cathode potential,
@a= closed circuit anode potential, and
R, = resistance of an individual anode.
For three-dimensional or space-frame type offshore
structures, anode resistance is normally the dominant
component of the total circuit resistance since its surface
area is much smaller that that of the structure; and so it
alone is considered. In most cases this term is calculated
from standard, numerical relationships presented in the
literature [9-151 that are based upon anode dimensions and
electrolyte resistivity. Figure. 1 graphically illustrates the
principle behind Equation 1 as a schematic polarization
curve for both anode and structure. In the case of
unidimensional structures (pipelines) and components
(cables), it may be necessary to consider also the metallic
path cathode resistivity.
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APPLIED CURRENT
Figure 1: Schematic illustration of the potential, current,
and resistance terms for cathodically polarized steel in sea
water.
From the net current for protection (Equation I), the
number of anodes required for protection, N, is determined
from the relationship
i, A ,
N=-
I,
where i, = cathode current density for polarization.
Application of this protocol requires that 4, be spatially
uniform. While this is likely to be the case for space frame
structures with distributed anodes, 4, normally varies with
position otherwise (ship hulls, pipelines, and cables, for
example).
111. Rapid Polarization Based Design
Historically, cp design was based upon a single
current density that polarized the structure to the potential
required for protection; that is, to -0.80 VAdAgcl, within
from several months to one year [16]. This relatively
lengthy period was a consequence of the design i, being
low such that development of surface films (calcareous
deposits) and associated oxygen concentration polarization
were slow. However, field surveys of structures with such
cp designs have often revealed potentials that were 100 to
250 mV more negative than -0.80 VAdAg,,,; and the life of
the cp system for these has often exceeded what was
projected in the initial design. For example, Evans [17]
reported that potential for several platforms in the Arabian
Gulf was on the order of -0.94 VAg/AgcI after 15 years,
although the original design was for only ten. Most of the
anodes on these structures had depleted, but apparently the
small current that continued to flow provided protection.
Similarly, Cochran [18] indicated that 77 of 100 platforms
protected by galvanic anodes exhibited potentials of -0.92
V A d ~ g or
l more negative. A 33 year cp system life was
estimated for one platform that exhibited potentials of from
-0.91 to -0.99 V A d A s C l after 4.5 years, whereas the original Production Typical Design Current Density,
design was for 20 years. Area mA/m2 (mA/ft2)
Initial I Mean 1 Final
The above observations can be explained by the
experiments of Cox [I91 who, some fifty-plus years ago,
Gulf of Mexico 110 (IO) 55 (5)
demonstrated that application initially of a relatively high
current density resulted in formation of calcareous deposits U.S. West Coast 150 (14) 90 (8)
that were particularly protective and yielded a lower Cook Inlet 430 (40) 380 (35)
maintenance or long-term current density than if the initial Northern North Sea 180 (17) 90 (8)
value for this parameter was low. Based either upon Southern North Sea 150 (14) 90 (8)
laboratory or service data, several authors [20-251 have Arabian Gulf 130 (12) 65 (6)
revisited during the past one-to-two decades the high initial Australia 130 (12) 90 (8)
current density concept; and this approach is now being
Brazil 180 (17) 65 (6) 90 (8)
employed routinely for cp system design of offshore
petroleum production structures. Accordingly, the current West Africa 130 (12) 65 (6)
recommended practices for marine cp design [6,7] address Indonesia 110 (10) 55 (5)
rapid polarization by application of a relatively high initial
current density (io), such that a structure potential in the number for each of the three current density criterion arises
range -0.90 to -1 .OO V A d A g C l results "...within a reasonably because the procedure is an algorithm rather than being
short period of time" [6]. The design also includes two first principles based.
other criteria, one based upon a mean current density (im)
and the other upon a final current density (9. Values for N The predominant cathodic reaction that occurs upon
to satisfy the requirement imposed by io and rj, No and Nr, metal surfaces in natural waters is oxygen reduction or
respectively, are determined using Equations 1 and 2,
where each of these current densities replaces i,. The 1
criterion upon which i/ is based intends to ensure that -0, + H 2 0 + 2 e ' 4 2 0 H - ; (4)
adequate anode mass remains at the end of the design life 2
to affect repolarization should this become necessary, The
however, at potentials negative to that of the reversible
mean current density, on the other hand, is the time-
averaged value over the design life and, as such, is hydrogen electrode water dissociation or the reaction
equivalent to the single current density employed in the
earlier protocol [16]. The number of anodes required to H,O+e* + -H,
1 +OH'
provide this current density, Nm,is calculated from the 2
relationship
also transpires. Figure 2 presents steady-state qLi, data
in, . A, -T from a series of experiments where cylindrical API Grade
"= c.w*u
7 (3) 42 steel specimens were galvanically coupled in natural sea
water to an aluminum anode ring through an external
resistor, the size of which varied for each test [25]. From
where
this, the reason for the beneficial effect of rapid
polarization is apparent in that the i, that ultimately resulted
T = design life,
from modest cathodic polarization, such that the protection
C = anode current capacity,
potential (-0.80 V A d A g c l ) that was achieved in the long-
w = weight of a single anode, and
term, was about 2.5 times greater than if the long-term
U = a utilization factor,
potential were near - 1 .OO V A ~ A ~ C I .The trend in Figure 2,
where i, increased with increasing cathodic polarization for
which, in effect, is a modified form of Faraday's law. The
potentials below about -1.00 VAdA6c1,was attributed to the
purpose of this calculation is to ensure that adequate anode
hydrogen reaction (Reaction 5). Thus, the optimum
mass is present for the cp system to achieve its design life.
situation is one where the steady-state potential of
Typical values for these three design current densities are
protected structures is in the range -0.90 to -1.05 V A d A g C b
listed in Table 2 [7]. Ideally, each of the three i, values
should yield the same N, however, this is normally not the
Cathodic protection design for marine pipelines,
case; and so the highest of the three is specified. For
which are invariably coated, involves determination of net
uncoated structures, this is invariably No.Accordingly, the
current demand, IC,according to
cp system may be over-designed in terms i, and i/. This
failure of the design procedure to yield a common anode

1789
 -0.69
-0.6C I
-0.7C- Presumably, the observation that potentials in the range
51
-?. -0.8C-
m
U
from -0.90 to -1.05 V A ~ A result
~ C ~ in the most protective
deposits (that is, in ones that are most impermeable to
oxygen ingress such that current density is minimum) is
-0.9C- caused, on the one hand, by those that form at more
0
positive potentials being relatively thin and at more
negative potentials becoming dislodged by hydrogen gas
generation. It is also possible that deposits that form
-i.id J outside the above potential range have a different
0 10 20 30 40 50 60 composition or microstructure, or both, and less protective
Current Density, mA/m2 properties.
Figure 2. Steady-state potential-current density relationship
for cathodically polarized steel in quiesent sea water. V. A Unified CP Design Equation
Fischer et al. [22] developed a first principles based
modification to Equation 1 as
where A, is pipe surface area and fc is the coating
breakdown factor (ratio of bare to total surface area).
Correspondingly,the net anode mass, M, is calculated from
a modified form of Equation 3 as where R, is the total circuit resistance. Thus, a linear
relationship between #, and i, with slope RI ' A , and
8,760-ic T vertical intercept &, is projected, provided R,,A,, and q&
M= (7)
u*c remain constant. The R, .A, term has been designated the
slope parameter, S. Equation (13) has now been verified
Current output per anode is determined from Equation (1) from both laboratory and field results by a number of
and the number of anodes from Equation (2). These are investigators [25,33-351.
equally spaced along the pipeline as bracelets.
In the case of space frame structures protected by
IV. Calcareous Deposits multiple galvanic anodes,

Any comprehensive effort to advance marine cathodic

protection practice must include an improved
understanding of the long-term &ic relationship (Figure 2),
the variables upon which it depends, and how and why it Several authors [33-351 have recently proposed that the
evolves. To this end, it is generally recognized that the approach to marine cp design documented in the current
minimum maintenance current density that results in the recommended practices for offshore structures [6,7] can be
potential range -0.90 to - 1.05 V A ~ / A is
~ Ca Iconsequence of improved upon by equating Equations (3) and (14) in terms
formation of a particularly protective calcareous deposit ofN. Thus,
[26-321. Such deposits occur as a consequence of
Reactions (4) and ( 5 ) displacing the inorganic carbon
equilibria, as expressed by the reactions

and this is termed the unified design equation. This

to the right such that pH in the vicinity of the cathode is
increased and calcium and magnesium rich compounds
precipitate according to
expression affords an advantage over the present approach
(Equations (1)-(3)) in that all terms on the right side are
known from the design choices; and so the process is
reduced to determination of the optimum combination of
Ra and w. This may be accomplished in terms of anodes of
standard dimensions or, altematively, by elongated anodes
or by duanodes [36]. The required number of anodes can
then be calculated from Equation (12). It has been shown
that cp design of a typical offshore structure based upon the
unified design equation yields a 32 percent reduction in
anode mass compared to design according to present

1790
recommended practices [6,7]. This arises because Equation
(1 5 ) is first principles based and incorporates both i, and io,
the former explicitly the latter implicitly via S. As such,
design can be optimized in terms of both parameters
instead of just one. An alternative view is that, of the two
terms on the left side of Equation (15), R, determines io
while w relates to i,.
VI. Impressed Current CP Systems
The slope parameter protocol has been extended to
the case of impressed current (ic) cp systems for offshore
structures [37]. This is based upon the relationship
where
E is rectifier voltage,
is potential of the ic anode,
E, is any lead wire voltage drop, and
E, is the voltage drop associated with the anode.
Substitution of Equation (1 3) into (16), yields
where q5a(eq) is the potential of an equivalent galvanic
anode that yields the same 4, as the impressed current
anode (determined by extrapolation of the &i, curve for
the ic system to zero current). By selecting a value for
&(eq), a lower bound to the polarized potential can be
established. A limitation of this method, however, is that
Equations (13), (14), and (17) assume that 4, is spatially
constant. This condition may be met for a space frame
structure protected by an ic system with remote anodes;
however, it is unlikely to be satisfied where anodes are in
close proximity to or mounted upon the structure (ship
hulls, for example). For such situations, an algorithm must
be developed whereby an equivalent 4, is identified.
VII. Application of the Slope Parameter Method
and a Unified Design Equation for Pipelines
Recently, a first-principles based design equation for
one-dimensional structures that are protected by identical
equally spaced galvanic anodes was derived [38] as
where
Tis the design life,
a is the cathode polarization resistance,
yequals l&,
1791
4co,ris the cathode free corrosion potential,
rp is the radius or equivalent radius on the
structure, and
La, is the spacing between anodes.
This expression has the advantage over the present
approach (Equation (7)) in that design can be accomplished
in terms of a specified potential (&. Also, current demand
of the structure, which is assumed to be coated, is included
as ay. Equation (1 8) constitutes an equivalent to Equation
(15) in that
Equation (1 8) is subject to the same limitation as Equations
(13), (1 6), and (1 7) in that a constant 4, is assumed. While
this is not restrictive in cases where anode spacing is
relatively small and polarization is adequate, significant
error occurs when this spacing is large or potential
attenuation is pronounced (metallic path resistance not
negligible).
The limitation of not being able to select an optimized
anode spacing has recently been overcome [39] from
development of a first-principles based attenuation
equation which includes all relevant resistance terms
(anode and metallic path), as well as polarization resistance
and coating quality. Thus,
where
E, is the magnitude of cathodic polarization,
z is distance along the pipe from an anode,
r, is the radius of a spherical anode superpositioned
upon the pipe,
H=- 'rp
R, . 2mp
B= , and
ay
p. is electrolyte resistivity.
Figure 3 presents Finite Difference Method (FDM)
solutions to this expression for different current demands
(values for ay) in the case of galvanic bracelet anodes
spaced 244 m apart on a 0.27 m diameter pipe in 0.30 !2m
water and compares these with Boundary Element
Modeling (BEM) results. Both solutions indicate that
potential attenuates rapidly within the first several meters
of the anode and is relatively constant thereafter. That the
FDM and BEM solutions are in excellent mutual agreement
is taken as qualification of Equation (20) in view of the
proven accuracy of BEM. By way of comparison, results
from the classical equation of Uhlig [40] are also shown
and are seen to be non-conservative. It is concluded that
Equation (20) provides a means for optimizing anode and
anode sled spacing on one dimensional structures. With
increased anode spacing, however, the FDM solution
shows additional attenuation, whereas the BEM, which
does not incorporate metallic path resistance, does not.
Figure 4 provides an example of this for L, = 6,000 m.
Here, Equation (20) provides the greater accuracy. Also,
this expression provides a method for optimizing anode
spacing.
ii,
2
3 -0.90
e -0.8
BP Amoco, Chevron, Exxon Mobil, Marathon, Minerals
Management Service, Shell, and Texaco.
IX. References
[I] Davy, H., Phil. Trans. Royal Soc. London, Vol. 114,
1824, p.151.
[2] Davy, H., ibid, Vol. I 14, 1824, p.242.
[3] Davy, H., ibid, Vol. 115, 1825, p.328.
[4] Graham, D. P., Cook, F. E. and Preiser, H. S., Trans.
Soc. Naval Arch. and Marine Engrs., Vol. 64, 1956,
p.24 1.
[SI Thomas, E. D., Lucas, K. E., Foster, Parks, R. L., and
Kaznoff, A. I., “Physical State Modeling of Impressed
Current Cathodic Protection Systems, paper no, 274
M presented at CORROSION/89, April 17-2 1, 1989,
New Orleans.
EEM
FDM I [6] “Cathodic Protection Design,” Dn V Recommended
Practice RP401, Det Norske Veritas Industri Norge
FDM AS, 1993.

FDM
[7] “Corrosion Control of Steel-Fixed Offshore Platforms
ay= 4 Associated with Petroleum Production”, NACE
Standard RP 01 76-94, NACE International, Houston,
-0.601 1 1994.
0 20 40 60 80 100 120 140
DISTANCE, m
[8] Uhlig, H. H. and Revie, R. W., Corrosion and
Figure 3: Comparison of attenuation results projected by 1) Corrosion Control, Third Ed., J. Wiley and Sons, New
Uhlig, 2) Boundary Element Modeling, and 3) a FDM York, 1985, pp. 223-228.
solution to Equation (20).
[9] Dwight, H. B., Electrical Engineering, Vol. 55, 1936,
-1.057 1 p. 1319.

$ -0.95
5
4
$ -0.85
i=
i5
I 4 FDM w/Ohmic
[10]Sunde, E. D., Earth Conduction Eflects in
Transmission Systems, Dover Publications, Inc., New
York, 1968.

[ 1 11McCoy, J. E., Transactions institute of Marine

Engineers, Vol. 82, 1970, p. 210.
& -0.75
&
[ 121Cochran, J. C., “A Correlation of Anode-to-Electrolyte
-0.65
Resistance Equations Used in Cathodic Protection,”
0 500 1000 1500 2000 2500 3000 paper no. 169 presented at CORROSION/82, March
DISTANCE FROM ANODE, m 22-26, 1982, Houston.
Figure 4: Comparison of attenuation projected by BEM and [ 131Strommen, R., Materials Performance, Vol. 24(3),
the FDM solution to Equation (20) for an anode spacing of 1985, p. 9.
6,000 m.
[14]Sunde, E. D., Earth Conduction Eflects in
VIII. Acknowledgment Transmission Systems, Dover Publications, Inc., New
York, 1968, p. 72.
The author is indebted to both past and present joint
industry funding sponsors from which this paper was
developed. Member companies and organizations include

1792
[ 151Cochran, J. C., “Additional Anode-to-Electrolyte
Resistance Equations Useful in Offshore Cathodic
Protection,” paper no. 254 presented at
CORROSION/84, April 2-6, 1984, New Orleans.
[ 161”Corrosion Control of Steel-Fixed Offshore Platforms
Associated with Petroleum Production“, NACE
Standard RP 01 76, NACE, Houston, 1976.
[17]Evans S., “Use of Initial Current Density in Cathodic
Protection Design”, Material Performance, Feb. 1988,
Vol. 27(2), p. 9.
[18]Cochran, J. C., “New Mathematical Models for
Designing Offshore Sacrificial Cathodic Protection
Systems”, paper no. 3858, Proceedings 1980 Offshore
Technologv Conference, May 5-8, 1980, Houston.
[ 191Cox, G. C., “Anticorrosive and Antifouling Coating
and Method of Application”, U.S. Patent 2,200,469,
1940.
[20]Foster, T., and Moores, V. G., “Cathodic Protection
Current Demand of Various Alloys in Sea Water,”
paper no. 295 presented at CORROSION/86, March
17-2, 1986, Houston.
[2 11Mollan, R. and Anderson, T. R., “Design of Cathodic
Protection Systems,” paper no. 286 presented at
CORROSION/86, March 17-2, 1986, Houston.
[22]Fischer, K. P., Sydberger, T. and Lye, R., “Field
Testing of Deep Water Cathodic Protection on the
Norwegian Continental Shelf,” paper no. 67 presented
at CORROSION/87, March 9-13, 1987, San Francisco.
[23]Fischer, K. P. and Finnegan, J. E., “Cathodic
Protection Behavior of Steel in Sea Water and the
Protective Properties of the Calcareous Deposits,”
paper no. 582 presented at CORROSION/89, April 17-
2 1, 1989, New Orleans.
[24] Schrieber, C. F. and Reding, J., “Application Methods
for Rapid Polarization of Offshore Structures,” paper
no. 381 presented at CORROSION/90, April 23-27,
1990, Las Vegas.
[25] Wang, W., Hartt, W. H., and Chen, S., Corrosion,Vol.
52, 1996, p. 419.
[26]Wolfson, S . L. and Hartt, W. H., Corrosion, Vol. 37,
1981, p. 70.
[27]Hartt, W. H., Culberson; C. H. and Smith, S . W.,
Corrosion, Vol. 40, 1994, p. 609.
[28]Lin, S-H and Dexter, S . C., Corrosion, Vol. 44, 1988,
p. 615.
1793
[29]Finnegan, J. E. and Fischer, K. P., “Calcareous
Deposits: Calcium and Magnesium Ion
Concentrations,” paper no. 58 1 presented at
CORROSION/89, April 17-21, 1989, New Orleans.
[30]Fischer, K. P. and Finnegan, J. E., “Cathodic
Protection Behavior of Steel in Sea Water and the
Protective Properties of the Calcareous Deposits,”
paper no. 582 presented at CORROSION/89, April 17-
2 1, 1989, New Orleans.
[31]Luo, J. S., Lee, R. U., Chen, T. Y.,Hartt, W. H. and
Smith, S . W., Corrosion, Vol. 47, 1991, p. 189.
[32]Mantel, K. E., Hartt, W. H. and Chen, T. Y.,
Corrosion,Vol. 48, 1992, p. 489.
[33] W. H. Hartt, S . Chen, and, D. W. Townley, “Sacrificial
Anode Cathodic Protection of Steel in Sea Water - Part
I1 Design and Data Analysis,” Corrosion, Vol. 54,
1998, p. 317.
[34] “Design of Galvanic Anode Cathodic Protection
Systems for Offshore Structures,” Draft Report from
NACE Task Group T7L- 16, NACE International,
Houston, November 14, 1997.
[35] Townley, D. W., “Unified Design Equation for
Offshore Cathodic Protection,” paper no. 97473
presented at CORFtOSION/97, March 9-14, 1997,
New Orleans.
[36]Burk, J. D., “Duanode Field Performance Evaluation
Cathodic Protection for Offshore Structures,” paper no.
309 presented at CORROSION/91, March 11-15,
1991. Cincinnati.
[37]W. H. Hartt, “The Slope Parameter Approach to
Marine Cathodic Protection Design and Its Application
to Impressed Current Systems,” Designing Cathodic
Protection Systems for Marine Structures and
Vehicles, Ed. H. P. Hack, ASTM STP 1370, American
Society for Testing and Materials, 1999, p. 1.
[38]K. Bethune and W. H. Hartt, “A Novel Approach to
Cathodic Protection of Marine Pipelines: Part I1 -
Applicability of the Slope Parameter Method,” paper
no. 00673 presented at CORROSION/OO, March 26-
3 1,2000, Orlando. To be published in Corrosion.
[39] P. Pierson, K. Bethune, W. H. Hartt, and P.
Anathakrishnan, Corrosion, Vol. 56,2000, p. 350.
[40]Uhlig, H. H., Corrosion and Corrosion Control, J.
Wiley and Sons, New York, 1962, pp. 42 1,422.