Documente Academic
Documente Profesional
Documente Cultură
Protection
Author: P.F. (Paul) Offermann
Abstract
The cost of corrosion in the U.S. in 1986 was estimated to be close to $180 billion.
Furthermore, estimates show that $70 billion worth of corrosion loss could have
been prevented in 1986 by applying modern corrosion control technology.
This section discusses the corrosion of metal in contact with moist soil or water, and
the tendency of some metals to corrode preferentially with respect to other metals
when located in the same environmental conditions. The use of a superimposed
current to prevent or reduce the rate of corrosion by making the entire metal surface
the cathode of an electrochemical cell and providing a separate anode is called
cathodic protection. This section discusses the mechanisms of cathodic protection
and the types of cathodic protection systems available for corrosion control. The
different types of cathodic interferences are covered along with the safety considerations. A glossary of cathodic protection terms is also included. Sections 1200-1600
discuss specific applications of cathodic protection systems.
The best cathodic protection system in the world is of no value if not properly
checked and maintained. See Section 1800 on maintenance for details.
Contents
Page
1100-3
1100-7
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1100-1
1100-9
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1100-12
1100-14
1100-17
1161 Change in pH
1162 Calcareous Coating
1163 Electro-osmosis
1170 Cathodic Interference
1100-18
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1100-23
1190 Glossary
1100-24
1191 References
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Corrosion of Iron
When iron is in contact with water solution containing (H+) and (OH-) ions, the iron
will tend to go into solution at anodic areas. At the anode, iron atoms lose electrons
and become positively charged iron ions which may combine with negatively
charged (OH-) ions in the solution to form, usually, ferrous hydroxide Fe(OH)2.
Ferrous hydroxide may react further to form ferric hydroxide Fe(OH)3, which is
familiar rust. The electrons migrate through the metal to the cathode.
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++)
Potential
-2.34
Aluminum (Al+++)
-1.67
++)
Zinc (Zn
-0.76
Chromium (Cr+++)
-0.71
++)
-0.44
Iron (Fe
Cadmium (Cd++)
-0.40
++)
Nickel (Ni
-0.25
Tin (Sn++)
-0.14
++
Lead (Pb )
-0.13
Hydrogen (H++)
0.00
0.242
0.288
0.315
Copper (Cu++)
0.34
Silver (Ag )
0.80
Platinum (Pt++)
1.20
Gold (Au
Note:
+++
1.42
The potentials vary with both concentration and temperature; in other concentration, these potentials
may deviate considerably from those shown. The standard electrode potential is not always a reliable
guide to the galvanic relationship of pairs of different metals. The above standard half cell potentials
are relative to a hydrogen electrode at 25C.
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Rate of Corrosion
The hydrogen atoms at the cathode tend to form a film on the surface of the cathode.
This film reduces the flow of the corrosion current and inhibits further corrosion.
This hydrogen is the basis of the polarization film commonly referred to in corrosion work. Therefore, the rate of corrosion will be governed by the rate of removal
of the hydrogen film. The hydrogen film can be removed by either of the following
reactions:
2H H2 (gas)
2H + 1/2 O2 H2O
The removal of the hydrogen as a gas requires that additional energy in the form of
an electrical potential be applied to the system to cause the hydrogen atoms to
combine to form gas molecules. This additional potential is called the hydrogen
over-voltage. Usually, this reaction does not take place in neutral solutions where
there is no externally applied voltage. However, there is sufficient energy available
in acidic solutions. For this reason, hydrogen gas normally is released when iron is
immersed in an acid solution.
In most neutral solutions, the second of the above reactions will control the rate of
corrosion of iron. Thus, in neutral solutions, the rate of corrosion is determined by
the availability of dissolved oxygen.
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Electrolytic Cell
An electrolytic cell is a type of corrosion cell consisting of two electrodes
immersed in an electrolyte with an external electromotive force applied between
them. The external potential will cause current to flow into the electrolyte from the
electrode (anode) connected to the positive terminal of the external source of power
and back to the power source through the electrode (cathode) connected to the negative terminal. The anode is made more positive with respect to the cathode by the
externally applied current.
This reversal of the polarity of the external terminals of an electrolytic cell, as
compared with a galvanic cell, is sometimes a source of confusion. To avoid confusion, remember that in any electrochemical cell, current always enters the electrolyte at the anode and leaves the electrolyte at the cathode.
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Electrochemical Equivalent
The rate of corrosion at the anode of any corrosion cell is a function of current flow
and the electrochemical equivalent of the anode material. The electrochemical
equivalent of an element may be defined as the weight of an element dissolved at
the anode or deposited at the cathode of an electrochemical cell by the passage of
unit quantity of electricity in a given time. In cathodic protection work, it is convenient to express this in pounds per ampere-year. The electrochemical equivalent of
iron for the normal corrosion reaction is 20 lb/amp-yr. For every ampere of current
discharged from an iron or steel structure in an electrolyte, 20 pounds of metal will
go into solution per year.
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connected such that the potentials and currents involved in the corrosion reaction
can be measured. A reference electrode is used to measure open-circuit anode
potential Eao and then the open-circuit cathode potential Eco with both switches
(S1 and S2) open. In this situation no corrosion current flows in the circuit. The open
circuit potentials are shown in Figure 1100-5.
Fig. 1100-4 Electrical Circuit
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When switch S1 is closed corrosion current Ia flows in the circuit. The magnitude of
this current can be varied with the adjustable external resistor R1. The anode potential Ea and the cathode potential Ec can be varied by adjusting the flow of corrosion
current Ia. Polarization gradually occurs on the electrodes (anode and cathode). This
polarization causes the potentials Ea and Ec to vary, altering the magnitude of corrosion current Ia for a fixed value of external resistance R1. The polarization voltage
always opposes the current flow.
When the electrodes (anode and cathode) are fully polarized, the external resistor R1
is reduced to zero. The magnitude of corrosion current Ia measured is the steady
state value. This occurs when the sum of the polarization potential drops at the
anode and the cathode is equal to the open circuit potential difference between the
anode and cathode (shown at point B in Figure 1100-5).
Ea + (-Ec) = Eao - Eco
(Eq. 1100-1)
The potential of the freely corroding system, Eb, then corresponds to equal polarized potentials of anode and cathode (including the voltage drops due to the flow of
current through the electrical resistance between electrodes and electrolyte as well
as potentials due to electrochemical reactions at the electrodes). In this case, the
cathode current Ic and anode current Ia are equal.
If switch S2 is closed, protective current Ip is applied to the system through the
cathodic protection anode. As the Ip current is increased, the corrosion current Ia
will decrease and the cathodic current Ic will increase. The cathodic current
Ic = Ia + Ip.
When complete protection is achieved, Ia = 0 and Ic = Ip. This is realized when
Ec = Eao.
In the case of large structures, complete protection is obtained when the entire
surface is polarized to the open-circuit potential of the most anodic area of the
structure.
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materials are magnesium, zinc, and aluminum alloys. Cathodic protection using a
sacrificial anode is represented schematically in Figure 1100-7.
Fig. 1100-6 Galvanic Series for Materials in a Typical Neutral Soil
Potential, volts vs Copper/Copper Sulfate
Electrode
Material
Mg-1.4 Mn
-1.75
91 Mg-6 Al-3 Zn
-1.55
Zinc
-1.1
95 Al-5 Zn
-1.05
Aluminum
-0.8
Steel (Clean)
-0.7
Steel (Rusted)
-0.3
-0.5
Lead
-0.5
-0.2
-0.2
-0.2
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Rectifiers
Batteries
Thermoelectric generators
Wind-driven generators
Engine-driven generators
Turbine-driven generators
Solar cells
Impressed current systems normally use anode materials which have low consumption rates (i.e., do not go into solution quickly). Some of these anode materials are
listed in Figure 1100-9. Materials having relatively high consumption rates (such as
aluminum, iron, and steel) are used under some circumstances.
The anodic reactions that occur at impressed current anodes involve both metal
dissolution and gas evolution. Typically, chlorine evolution predominates in saline
environments and oxygen evolution predominates in neutral soil and fresh water
environments.
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Fig. 1100-10 Approximate Cathodic Protection Current Requirements for Bare Steel
Electrolyte
Current Density
Remarks
500 A/ft2
50
25100 mA/ft2
510 ft/sec
15
25 mA/ft2
35 ft/sec
Sea Water
515 mA/ft2
Sea Water
5 mA/ft2
1020 mA/ft2
5 mA/ft2
Fresh Water
25 mA/ft2
Initial requirement
Polarized (calcareous coating)
Well aerated
Deaerated
Well aerated
Soil
12 mA/ft
Soil
0.11 mA/ft2
This reaction reduces polarization, increasing the current requirement. For this
reason, structures in well-aerated soils such as sand and gravel require greater
cathodic protection current than structures surrounded by deaerated soils such as
clay and muck.
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The above reaction does not occur at structure anodic areas or on the surface of
sacrificial anodes. In most sea water environments the chlorine gas easily escapes
and therefore does not cause significant anodic polarization. On the other hand, in
saline soils, anodic polarization occurs unless the produced gas is allowed to escape
through vents or carbonaceous backfills around the anode. As a result of the polarization, the voltage increases to maintain the same current.
Salt also reduces the electrical resistivity of soil, which increases the current
required to protect the structure.
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There are several criteria for determining if a structure has adequate cathodic
protection. Once a testing method is adopted, it should continue to be used. The
following methods are discussed:
Potential Criterion
Polarization Shift Criterion
Potential
Criterion mV vs Cu/CuSO4
-850
-950
Lead
-700
Copper
-500
Aluminum
-950
Potential criteria are less valid as temperature increases and must be adjusted more
electronegatively to compensate. More electronegative potentials are also required if
anaerobic bacteria activity exists.
In a structure cathodically protected by an impressed current system, the voltage
drop can be minimized by turning off the power supply and immediately taking
steel-to-soil potential measurements. The surface potential does not change immediately when the power source is removed. Hence, an instantaneous off measurement is a true indication of steel-to-soil potential. The reason for reading potential
instantaneously is that the structure begins to depolarize with time. This technique
has the added advantage that the metallic path voltage drop in the external circuit is
also eliminated. On structures having multiple current sources influencing the
potential reading it may be difficult to interrupt all the sources simultaneously.
(Refer to Section 1700 for more information on Instant-off testing.)
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When multiple current sources cannot be interrupted simultaneously, sound engineering practice should be used to assess measurement errors from voltage drops
(other than those across the structure to electrolyte boundary). Sound engineering
practice includes:
evaluating the physical and electrical characteristics of the pipe and its
environment,
Raise the polarized potential at least 100 mV over the base (static) potential.
Static potentials are pipe to soil potentials measured before the energization of
the cathodic protection system. If the polarized potentials, measured at the same
locations as the recorded static potentials, are greater than a 100 mV electronegative shift, this criterion has been satisfied. Since polarization is a function of
time, on bare structures it is recommended that the cathodic protection system
be energized for a period of time before conducting the polarized potential
survey.
It is also necessary that all potentials measured after energization be free of
ohmic voltage drop (by momentarily disconnecting the power source and
taking potential measurement) so that a valid comparison to the base corrosion
potentials can be made. (See previous discussion on Potential Criterion.) If
baseline corrosion potential data were not recorded prior to energization, the
cathodic protection system can be turned off to allow the structure to depolarize to obtain the baseline data. The disadvantage of this is that the structure
could remain unprotected for an extended period of time.
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2.
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protection on the surface of the metal are considerably decreased. See Section 1400
for additional information.
1163 Electro-osmosis
Electro-osmosis is frequently associated with cathodic protection. This effect causes
a conductive solution to flow through a porous membrane or a capillary opening
filled with the solution when an electric current passes through the membrane or
capillary opening. The direction of flow is toward the cathode.
Electro-osmosis may occur at anodes in certain types of clay soils (and at cathodes
with permeable coatings). Electro-osmosis is undesirable because it drives moisture
away from the anode. In some cases, the soil around the anode may be dried to the
point that its conductivity is seriously reduced. This results in an excessively high
anode resistance and a reduction in the flow of protective current. At the cathode,
the reverse effect occurs; moisture tends to flow toward the cathodically protected
surface. If the surface is covered by a permeable paint or coating, the penetration of
moisture will be accelerated by electro-osmosis; the bond between the coating and
the surface may be loosened, and the coating may be damaged.
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Corrosion may be observed at locations where stray currents leave the structure
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Cathodic protection system interference due to stray currents are of two types:
Anode field
Cathode field
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The stray current discharge area normally is in the vicinity of the transit system
substation. Where multiple substations operate, stray currents may transfer from one
substation to another.
On ductile and cast-iron piping, which is often electrically discontinuous, the stray
current can discharge around discontinuities (e.g., at each bell and spigot joint),
causing corrosion damage.
Welding Equipment
Electric welding equipment is another source of stray dc current. It is common practice to ground one welding electrode to a metallic structure at the construction site.
This superimposes dc stray current on the buried metallic structure (such as a pipeline or tank). Considerable corrosion is observed at discharge points of the buried
structure where the stray current leaves the structure.
Offshore platforms have reported corrosion damage caused by welding operations.
This damage occurs during the time the welding machines are mounted on a barge
or vessel with the machines negative ground attached to the vessel and the positive
electrode used for welding.
Cathodic shielding
Galvanic anodes
Electrical bonding
Application of coatings to stray current pick-up areas on the foreign structure or coating the cause of the interference
Removal of Source
Although unacceptable in most cases, the most effective method of preventing stray
current interference is to remove the source.
Some possible solutions for interference source:
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HVDC systems can be operated in a bipolar mode, with a minimum of imbalance, or total time of monopolar operations can be limited
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Cathodic Shielding
Interference damage can be minimized by reducing stray current flow. The technique of cathodic shielding can be used to prevent much of the stray current from
entering the foreign structure. A bare metal shield is connected to the negative
terminal of the rectifier, providing a very low resistance shunt path for the stray
current. This method is effective for structures of amphoteric materials such as
aluminum, zinc and lead which can be damaged at both pick-up and discharge sites.
Amphoteric materials corrode at high rates in both basic and acidic environments.
Galvanic Anodes
Galvanic anode(s) can be installed at current discharge locations on the interferedwith structure (particularly at crossings with the interfering structure). These anodes
provide a lower-resistance path that is more negative than the structure. This
provides a path for the discharge of the stray current because of the relatively low
resistance of the anodes when compared to the structure.
Care must be taken in designing galvanic anode mitigation systems since the
cathodic protection current as well as the stray current must be taken into account
when calculating the galvanic anode life.
Electrical Bonding
An electrical conductor is installed between the interfered-with and interfering
structure at a mutual crossing to mitigate dc interference. See Section 1800 for more
information on bonding.
Forced drainage bonds are utilized for draining dc stray currents by inserting a dc
source in series with the bond. This is often used in electric traction systems for
mitigating dc interference.
Protective Coatings
The application of a protective coating to the stray current pick-up sites on the interfered-with or interfering structure will reduce the magnitude of stray current dramatically. This method is effective but expensive after the structure installation. Cost is
minimized if protective coatings are provided during the design stage.
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Electrostatic induction
Electromagnetic induction
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Resistive coupling
Electrostatic Induction
A structure close to an ac power line acts as one side of a capacitor with respect to
ground. This situation often occurs with pipelines supported on skids.
Electromagnetic Induction
A structure close to an ac power line acts as single-turn secondary of an air-core
transformer in which the overhead power line is the primary. Structures both above
and below ground can be affected. Heavily loaded single phase ac distribution
power lines produce significant ac stray currents.
Interference currents of an ac origin can be identified easily by measuring the structure ac voltage-to-ground potential. The reference electrode used for cathodic
protection measurements can be utilized as the ground contact.
Resistance Coupling
During power line faults to ground, large ac currents are transmitted to Earth and
nearby underground structures. These currents have large magnitudes (in the range
of several thousand amperes) that can cause substantial physical damage to the
structure coating. In extreme cases where the current density is high, steel piping
has been known to melt.
Even with distributed anodes, hazardous voltages still may exist at the separation
points and require more extensive sacrificial anode installations to reduce the ac
voltage to 15 volts or less.
Corrosion personnel must be made aware of potential shock hazards on a structure
subjected to high voltages due to ac coupling. Other precautions that can be taken
include:
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The anode cable, drainage cable, or a bond is severed while the dc power
source is operating, particularly if there is no low-resistance current path in
parallel with the severed cable
When two cables carry current in parallel, significant sparks usually will not occur
when one of the cables is broken. Similarly, where two or more parallel pipelines
are bonded together in a cathodic protection system, the hazard in either opening the
line or short-circuiting insulating flanges is minimized.
Precautions
The following precautions should be observed when working with impressedcurrent cathodic protection systems where flammable vapors may exist:
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The edges of insulated flange assemblies should be covered with electrical tape
to minimize accidental short-circuiting of the flange
Before a cathodically protected line is cut or a flange (not insulated) in the line
is opened, a bonding wire should be connected across the section of the line to
be opened, after the nearest cathodic protection power supply on each side of
the section to be opened is turned off
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The dc potentials involved in cathodic protection systems usually are so low that no
electric shock hazard exists.
Shock hazard exists on structures subjected to ac interference. Shock hazards are
decreased by incorporating nonmetallic dead-front test stations with a cathodic
protection system. DC rectifiers of impressed current systems should be protected
from ac fault currents with devices such as capacitors and metal oxide varistors.
Contact a qualified electrical engineer for more information.
1190 Glossary
anode: 1: the electrode of an electrochemical cell at which oxidation occurs
(electrons flow away from the anode, conventional current toward the anode in the
normally metallic external circuit; the anode is usually the electrode where corrosion occurs and metal ions enter solution) 2: in cathodic protection, an electrode that
discharges current to the electrolyte, where it flows to the cathodically-protected
surface
anode bed: see ground bed
anode cable: in an impressed-current cathodic-protection system, the cable from the
positive terminal of the dc power source to the ground bed
anode field: the electric field in the electrolyte around an anode or ground bed
generated by the flow of current from the anode through the electrolyte
anode lead: the insulated wire or cable connected to an individual anode
attenuation: the decrease of current and voltage with distance from the drain point
on a cathodically-protected pipeline
backfill: low-resistivity material placed around an anode
bond: see continuity bond
casing: (pipelines) a larger pipe through which the pipeline passes, sometimes
installed at road and railroad crossings
casing: (wells) a tubular used in oil, gas, and water wells to isolate various downhole formations from the well bore
cable: a flexible, insulated electrical conductor (or group of conductors)
cathode: an electrode at which electrochemical reduction of its surface or some
component of the electrolyte occurs; in a cathodic protection system, the cathode is
the cathodically protected surface
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cathode field: the electric field in the electrolyte around a cathode or cathodically
protected structure generated by the flow of current through the electrolyte to the
cathode
cathodic disbondment: the coating disbondment caused by the products of a
cathodic reaction
cathodic polarization: the change of electrode potential in the electronegative
direction resulting from current transfer between the electrolyte and electrode
coating: a dielectric material applied to a structure to separate it from the
environment
coating disbondment: the loss of adhesion between a coating and the structure
surface
conductor: a material, bare or insulated, suitable for carrying an electric current
continuity bond: an intentional metallic connection that provides electrical
continuity
corrosion: the deterioration of a material, usually a metal, by reaction with its
environment
corrosion potential: the mixed potential of a freely corroding metal surface with
reference to an electrode in contact with the electrolyte
corrosion rate: the rate at which corrosion proceeds, expressed as either weight loss
or penetration, per unit time
criterion: standard for assessment of the effectiveness of a cathodic protection
system
current: in this manual current means conventional current, i.e., the reverse of electron flow. Electrons flow away from the anode, conventional current flows toward
the anode in the normally metallic external circuit. The anode is usually the electrode where corrosion occurs and metal ions enter solution.
current density: the current per unit area
current span: a length of pipe of uniform cross-section between two test leads
(usually 100 to 200 feet apart or more) used to determine current flow by measuring
voltage drop
deep ground bed (or deep-well ground bed): one or more anodes installed vertically at a depth of 50 ft or more below the Earths surface in a drilled hole, for the
purpose of supplying cathodic protection current
depolarization: reduction or elimination of polarization by physical means or by
change in environment
drain cable: the conductor, connected to a cathodically protected structure, through
which current flows from the structure to the negative terminal of a dc power
source, or to a galvanic anode
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drain point: the point on a cathodically protected structure where the drain cable is
connected
dual casing: two concentric casing strings
electrode: an electronic conductor used to establish electrical contact with an electrolyte part of a circuit
electro-osmosis: passage of a charged particle through a membrane under the influence of a voltage; soil and coatings may act as the membrane
electrolyte: a chemical substance or mixture containing ions that migrate in an electric field; in this manual, the soil or liquid, including the moisture and other chemical contained therein, adjacent to and in contact with a buried or submerged
metallic structure
foreign structure: any structure that is not intended as a part of the system to be
protected
galvanic anode: a metal which, because of its relative position in the galvanic
series, provides protection to metal or metals that are more noble in the series, when
coupled in an electrolyte
galvanic cell: a cell in which chemical change is the source of electric energy,
usually consisting of two dissimilar conductors in contact with each other and with
an electrolyte or two similar conductors in contact with each other and with dissimilar electrolytes
galvanic series: a list of metals and alloys arranged according to their relative
potentials in a given environment
ground bed: one or more anodes installed in the Earth or water to supply cathodic
protection current
half cell reference electrode: see reference electrode
holiday: a discontinuity in a coating
impressed current: direct current supplied by a cathodic protection system utilizing
an external power source
instant-off potential: a structure-to-electrolyte potential measured immediately
after the protective current is interrupted
interference: any electrochemical disturbance on a structure as a result of stray
current
interference bond: a metallic connection designed to control electrical current
interchange between metallic systems
IR drop: the voltage across a resistance, expressed in Ohms Law
line current: the direct current flowing on a pipeline
lead wire: an insulated metallic connecting wire
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local cell: a galvanic cell resulting from differences between adjacent areas on a
metal surface in an electrolyte; these differences may be physical or chemical, either
in the metal or its environment
mixed potential: a potential resulting from two or more electrochemical reactions
occurring simultaneously on one metal surface
open-circuit potential: the measured potential of an electrode from which no
current flows
oxidation: loss of electrons by a constituent of an electrochemical reaction
oxygen scavenger: a chemical used to react with or remove dissolved oxygen
pipe-to-electrolyte potential: the difference in potential between the pipe and electrolyte, measured with reference to an electrode in contact with the electrolyte; also
called pipe-to-soil potential, pipe-to-water potential
polarization: the deviation from the corrosion potential of an electrode resulting
from the transfer of current between the electrode and the electrolyte
polarization tests: the procedure of taking pipe-to-soil potentials at different time
intervals after cp has been applied to determine the effect of time on readings
obtained
protective current: dc current picked up by the protected structure from the
electrolyte
rectifier: a device for converting alternating current to direct current
reduction: gain of electrons by a constituent of an electrochemical reaction
reference electrode: a reversible electrode with a potential that may be considered
constant under similar conditions of measurement (examples: saturated coppercopper sulfate, saturated calomel, and silver-silver chloride)
remote cell: a reference electrode placed in an area over which the IR drop in a
pipe-to-soil reading is constant
remote earth (or remote soil): earth sufficiently removed from a cathodic protection system that the potential is not sufficiently affected by the operation of the
cathodic protection system
resistivity: the resistance measured between two parallel faces of a cube of the
substance under consideration (the usual unit is ohm-centimeters, the resistance, in
ohms, of a cube one centimeter on a side)
reworks: the work done to a well to restore production. May include pulling casing,
tubing rods, and pump
sacrificial anode: see galvanic anode
shallow ground bed (or surface ground bed): a ground bed installed at a depth of
less than 50 feet (usually less than 10 feet)
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1191 References
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1.
2.
3.
Pipeline and Gas Journal Staff Corrosion Control Report February 1988.
4.
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5.
6.
NACE International RP-0169-92, Control of External Corrosion on Underground or Submerged Metallic Piping Systems. NACE International.
7.
8.
9.
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