How Does Steel Corrode in Water?

To understand cathodic protection one must first understand the corrosion mechanism. For corrosion to occur,
three conditions must be present.

1. Two dissimilar metals

2. An electrolyte (water with any type of salt or salts dissolved in it)
3. A metal (conducting) path between the dissimilar metals

The two dissimilar metals may be totally different alloys, such as steel and aluminum, but are more usually
microscopic or macroscopic metallurgical differences on the surface of a single piece of steel.

If the above conditions exist, at the more active metal surface (in this case we will consider freely corroding
steel which is non uniform), the following reaction takes place at the more active sites: (two iron ions plus four
free electrons)
2Fe => 2Fe++ + 4e-

The free electrons travel through the metal path to the less active sites where the following reaction takes place:
(oxygen gas converted to oxygen ion - by combining with the four free electrons - which combines with water to
form hydroxyl ions)
O2 + 4e- + 2H20 => 4 OH-

Recombinations of these ions at the active surface produce the following reaction, which yields the iron corrosion
product ferrous hydroxide: (iron combining with oxygen and water to form ferrous hydroxide)

2Fe + O2 + 2H2O => 2Fe (OH)2

This reaction is more commonly described as 'current flow through the water from the anode (more active site)
to the cathode (less active site).

How Does Cathodic Protection Stop Corrosion?

Cathodic protection prevents corrosion by converting all of the anodic (active) sites on the metal surface to
cathodic (passive) sites by supplying electrical current (or free electrons) from an alternate source.

Usually this takes the form of galvanic anodes, which are more active than steel. This practice is also referred to
as a sacrificial system, since the galvanic anodes sacrifice themselves to protect the structural steel or pipeline
from corrosion.

In the case of aluminum anodes, the reaction at the aluminum surface is: (four aluminum ions plus twelve free
electrons)
4Al => 4AL+++ + 12 e-

and at the steel surface, (oxygen gas converted to oxygen ions which combine with water to form hydroxyl ions)

3O2 + 12e- + 6H20 => 12OH-

As long as the current (free electrons) is arriving at the cathode (steel) faster than oxygen is arriving, no
corrosion will occur.

Figure 1: Sacrificial anode system in seawater

Basic Considerations When Designing Sacrificial Anode Systems
The electrical current which an anode discharges is controlled by Ohm's law; that is:

I=E/R

I= Current flow in amps

E= Difference in potential between the anode and cathode in volts
R= Total circuit resistance in ohms

Initially current will be high because the difference in potential between the anode and cathode are high, but as
the potential difference decreases due to the effect of the current flow onto the cathode, current gradually
decreases due to the polarization of the cathode. The circuit resistance includes both the water path and the
metal path, including any cable in the circuit. The dominant value here is the resistance of the anode to the
seawater.
For most applications the metal resistance is so small compared to the water resistance that it can be ignored.
(Not true for sleds, or long pipelines protected from both ends). In general, long thin anodes have lower
resistance than short fat anodes. They will discharge more current, but will not last as long.

Therefore a cathodic protection designer must size the anodes so that they have the right shape and surface
area to discharge enough current to protect the structure and enough weight to last the desired lifetime when
discharging this current. As a general rule of thumb:

Length of the anode determines how much current the anode can produce, and consequently how
many square feet of steel can be protected.

Cross Section (Weight) determines how long the anode can sustain this level of protection.

Impressed Current Cathodic Protection Systems

Due to the high currents involved in many seawater systems it is not uncommon to use impressed current
systems. Impressed current systems use anodes of a type that are not easily dissolved into metallic ions, but
rather sustain an alternative reaction, oxidization of the dissolved chloride ions.
2Cl- => Cl2 + 2e-
Power is supplied by an external DC power unit..

Figure 2: Impressed current cathodic protection system in seawater

How Do We Know When We Have Enough Cathodic Protection?
We know whether or not we have enough current by measuring the potential of the steel against a standard
reference electrode, usually silver / silver-chloride (Ag/AgCl sw.), but sometimes zinc (sw.).

Current flow onto any metal shifts its normal potential in the negative direction. History has shown that if steel
receives enough current to shift the potential to (-) 0.800 V vs. silver / silver chloride (Ag / AgCl), the corrosion
is essentially stopped.

Due to the nature of the films which form, the minimum (-0.800 V) potential is rarely the optimum potential,
and designers try to achieve a potential between (-) 0.950 V and (-) 1.000 V vs. Ag/AgCl sw.
Figure 3: Protected vs Unprotected structures as verified by cathodic protection potential

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Impressed current cathodic protection systems for Understand

reinforcing steel- in- concrete corrosion
Top myths dispelled
CPT’s mission is to provide scientifically proven long-term
corrosion protection with integrity and innovation. CPT’s Featured Projects
experience in implementing impressed current cathodic protection
systems on millions of square feet and thousands of balconies have 2100 Towers
given us singular insight to what works and what doesn’t. Atlantic Ocean Club
Mainsail
Although there are many options in the market place today – NACE
(National Association of Corrosion Engineers) and the DOT
(Department of Transportation) are independent organizations that support the fact that only
impressed current cathodic protection is designed to STOP ongoing concrete craking and
spalling due to corrosion of reinforcing steel. CPT's manufacturer, Matcor, leads the industry in
innovative development of cathodic protection technology for reinforcing steel in concrete
structures. Matcor designed the first impressed cathodic protection system for a concrete bridge
deck in 1975 and today, hundreds of buildings and support structures, highway surfaces and
bridge decks, parking garages, marine and other concrete structures are protected by their
cathodic protection systems and products.
Every structure has its own unique characteristics due to location, construction methods,
previous repairs, and corrosion problems. Because of this, we design and manufacture a number
of steel-in-concrete cathodic protection systems using impressed current anodes to fit a wide
variety of situations. Impressed current cathodic protection systems from CPT are not simply
materials delivered to the job site. The systems include all components, installation drawings and
instructions, on-site technical assistance, written reports and documentation, final system
commissioning/energizing and maintenance instructions for system monitoring and monthly data
analysis.

Systems available for the Condominium market include:

Conductive Coating System-CPBD™-III

This system is the most cost efficient and applicable solution for Condominium balconies,
walkways, stair wells, plaza deck and parking garages. A non-wearing surface, easily applied
with a roller, brush or spray, the CPBD™ -III System is ideal for horizontal and vertical surfaces.
The surface of the system can be finished in a variety of textures and colors and is therefore an
excellent choice for building facades, balconies and garage ceilings.

Saw Slot System-CPBD™-II

The CPBD™ -II has proven to be durable and reliable. This system is usually specified for
vertical columns and parking garage decks. The high strength conductive concrete used in the
saw slots can be the final driving surface or, where required, covered with an overlay.

MMO Mesh Anode System-CPBD™

Our Mesh Anode system can be used for parking garages, sea walls, ramps and other structures.
The titanium mesh is embedded in new concrete or placed in an overlay on existing concrete. 

Impressed Current Cathodic Protection

Impressed current cathodic protection systems use an outside source of power to drive the
current from the anode to the cathode. The source of power for our system comes from
alternating current (AC) that we convert to DC current via a rectifier. Impressed current systems
are commonly used where the current requirements for corrosion protection are high and where
the driving voltage is greater than what can be obtained with galvanic systems.

These systems are more accurate and can be controlled to deliver just enough protective current
to the structure. Because we can control and measure it, we are confident that a 25 year design
life is achievable.

Cathodic Protection (CP)

The science of cathodic protection (CP) was born in 1824, when Sir Humphry Davy made a
presentation to the Royal Society of London: "The rapid decay of the copper sheeting on His
Majesty's ships of war, and the uncertainty of the time of its duration, have long attracted the
attention of those persons most concerned in the naval interest of the count. ... I entered into an
experimental investigation upon copper. In pursuing this investigation, I have ascertained many
facts ... to illustrate some obscure parts of electrochemical science... seem to offer important
application." Davy succeeded in protecting copper against corrosion from seawater by the use of
iron anodes.

From that beginning, CP has grown to have many uses in marine and underground structures,
water storage tanks, gas pipelines, oil platform supports, and many other facilities exposed to a
corrosive environment (see Corrosion Costs Study findings). Recently, it is proving to be an
effective method for protecting reinforcing steel from chloride-induced corrosion. (reference)

History of Cathodic Protection

Cathodic protection has become a widely used method for controlling the corrosion deterioration
of metallic structures in contact with most forms of electrolytically conducting environments,
i.e. environments containing enough ions to conduct electricity such as soils, seawater and
basically all natural waters. Cathodic protection basically reduces the corrosion rate of a metallic
structure by reducing its corrosion potential, bringing the metal closer to an immune state.  From
a thermodynamics point of view, the application of a CP current basically reduces the corrosion
rate of a metallic structure by reducing its corrosion potential towards its immune state as shown
here for iron and steel or here for aluminum and its alloys.

Cathodic Protection Basics

Corrosion Costs and Preventive Strategies Study

The cost of cathodic protection of metallic structures subject to corrosion can be divided into the
cost of materials and the cost of installation and operation. Industry data have provided estimates
for the 1998 sales of various hardware components totaling $146 million. The largest share of
the cathodic protection market is taken up by sacrificial anodes at $60 million, of which
magnesium has the greatest market share. Major markets for sacrificial anodes are the water
heater market and the underground storage tank market.

The costs of installation of the various cathodic protection (CP) components for underground
structures vary significantly depending on the location and the specific details of the
construction. For 1998, the average total cost for installing CP systems was estimated at almost
one billion (range: $0.73 billion to $1.22 billion). The total cost for replacing sacrificial anodes
in water heaters and the cost for corrosion-related replacement of water heaters was estimated at
$1.24 billion per year; therefore, the total estimated cost for cathodic and anodic protection is
$2.22 billion per year. (reference)

Groundbed Design
For underground structures requiring cathodic protection, the location and nature of the site where the
anode is placed needs careful consideration. A low soil resistivity, which would otherwise be classified as
a highly corrosive soil, is not the only factor which determines the location of the anode. Other factors
to be considered include the presence of foreign metallic structures, accessibility and availability of a
power source. The location which is specifically prepared to house a single or a combination of anodes is
called a groundbed.

 Impressed anode groundbeds: Once a location is selected and the soil resistivity is determined,
the engineer needs to design the type of groundbed and choose anode material and
combination. Types of groundbeds are classified as: shallow vertical, shallow horizontal or deep
well. Anode materials used for underground impressed current systems are generally graphite
or high silicon cast iron. In the groundbed, it is preferred for the anode to be surrounded by a
carbonaceous backfill. The backfill particles help to reduce anode resistance to earth, extend
anode life by allowing anodic reactions to occur on their surface and provide a porous structure
so the gases produced can escape.

o Shallow Vertical Groundbed: The individual or multiple anode groundbed resistances

can be determined using Dwight formula or can be determined graphically.

o Shallow Horizontal Groundbeds: Sometimes due to unfavorable soil conditions shallow

horizontal groundbeds are preferred. Again earth resistances can be determined by
calculation.

o Deep Well Groundbeds: Where soil resistivity at the surface are very high, a series of
vertical anodes are sometimes installed in deep well groundbeds (up to 100 m and more
deep). To determine the depth of the well it may be necessary to carry out a soil
resistivity survey. Using the four-pin method, soil resistivity variation with depth can be
determined by changing the pin spacing. Deep well groundbeds can take different
forms.

A basic design incorporates the use of a steel casing to prevent the collapse of the drilled hole. Several
anodes attached together with a rope are placed inside the casing. The remaining space is then filled
with carbonaceous material. Once the groundbed becomes operative the steel casing will be consumed.
After the pipe corrodes away the anode and backfill become active. Deep wells are generally fitted with
a vent to allow gases to escape. Gas entrapment tends to increase the groundbed resistance. It should
be added that in certain rock formations anodes have been installed satisfactorily without a steel casing.
Although deep well groundbeds provide good current distribution they are expensive to construct
because of the cost of the drilling. Careful design is also necessary because anode failures cannot be
easily rectified.

 Sacrificial Anode Groundbeds: In certain situations, for example in reducing stray current effects,
a sacrificial system may be specified to protect underground structures. The backfill used with
these anodes is different from that described for impressed anodes. A typical backfill contains a
mixture of clay and gypsum. The function of this chemical backfill to provide conditions
 favorable to anode dissolution. It also helps to reduce the groundbed resistance. Groundbed
resistances can be calculated using the same procedure adopted for impressed current anodes.
Individual galvanic anodes in a horizontal groundbed are generally not used. For this type of
groundbed a continuous galvanic anode strip is found to be practical.

 Remote and Close Groundbeds: Since a groundbed is a source of current, there is a field
(potential) gradient associated with it. When the voltage gradient in the soil near the structure is
far from the voltage gradient of the groundbed, the groundbed is referred to as remote.
However when the voltage gradient in the soil near the structure overlaps with that of the
groundbed, the groundbed is referred to as close. This is because the groundbed is near enough
to interfere significantly with the field gradient around the structure.

Impressed Current Cathodic Protection (ICCP)

Impressed current cathodic protection is applied by coupling the metal to be protected to the
negative pole of a direct current (DC) source (schematic), while the positive pole is coupled to
an auxiliary anode. Since the driving voltage is provided by the DC source there is no need for
the anode to be more active than the structure to be protected. There are basically three types of
anode materials:

 Inert or non consumable anodes

 Semi-consumable anodes

 Consumable anodes

All items to be protected shall be electrically connected and should have a welded or brazed
connection to an anode. For bolted or clamped assemblies without an all welded brazed electrical
grounding, the electric resistance should be less than 0.10 ohm. Coating on contact surfaces shall
be removed prior to assembly.

Protective Current Requirements in CP design

Assumptions of protective current requirements and bare metal areas. To obtain a starting point,
certain general assumptions have been found helpful: (reference)

 For bare metal in the ground, a current of 11 to 22 mA/m2 of bare metal surface has been
found adequate, except under extreme or unusual conditions. This value must then be
modified to suit the particular conditions.

 For coated pipe, the current required is difficult to estimate without field tests. The
primary reason is the unknown condition of the protective coat which can vary from
nearly 0% to 98% coverage. For a fairly new protective coat properly applied,. assume 2
 percent bare and 22 mA/m2 for use in tentative calculations. Field test may show that this
figure should be modified.

 Bare pipelines can usually be protected by 11 to 22 mA/m2. This is seldom justifiable

economically for extensive or long lines, however, and the necessary protection is usually
afforded by the application of cathodic protection to localized areas called "hot spots."

 Bare steel tanks are treated the same as bare pipelines. Inside steel surfaces in contact
with fresh water at zero or low velocities require from 22 to 65 mA/m2, depending on the
nature of the water. The low value is used for water which is scale forming. That is, the
water will form a calcareous coating on the surface of the metal.

 Protecting steel surfaces in contact with water in motion presents another problem. Water
in motion produces a scouring effect which prevents the formation of the above-
mentioned coating and even the formation of a hydrogen film. Therefore, surfaces
exposed to water in motion require a higher current density. The amount required is hard
to predict. In this case, an experimental determination of the current requirement should
be made.

 Protective Metallic Coatings

 Metallic coatings provide a layer that changes the surface properties of the workpiece to
those of the metal being applied. The workpiece becomes a composite material exhibiting
properties generally not achievable by either material if used alone. The coatings provide
a durable, corrosion resistant layer, and the core material provides the load bearing
capability. The deposition of metal coatings, such as chromium, nickel, copper, and
cadmium, is usually achieved by wet chemical processes that have inherent pollution
control problems. (corrosion costs study)

 See how our Sponsor can help you with galvanized testing and evaluation

 Alternative metal deposition methods have replaced some of the wet processes and may
play a greater role in metal coating in the future. Metallic coatings are deposited by
electroplating, electroless plating, spraying, hot dipping, chemical vapor deposition and
ion vapor deposition. Some important coatings are cadmium, chromium, nickel,
aluminum and zinc.Plating and surface treatment processes are typically batch operations,
in which metal objects are dipped into and then removed from baths containing various
reagents to achieve the desired surface condition. The processes involve moving the
object being coated through a series of baths designed to produce the desired end product.
These processes can be manual or highly automated operations, depending on the level of
sophistication and modernization of the facility and the application.

 Corrosion Costs and Preventive Strategies Study

  The most widely used metallic coating method for corrosion protection is galvanizing,
which involves the application of metallic zinc to carbon steel for corrosion control
purposes. Hot-dip galvanizing is the most common process, and as the name implies, it
consists of dipping the steel member into a bath of molten zinc. Information released by
the U.S. Commerce Department in 1998 stated that about 8.6 million metric tons of hot-
dip galvanized steel and 2.8 million metric tons of electrolytic galvanized steel were
produced in 1997. The total market for metallizing and galvanizing in the United States is
estimated at $1.4 billion. This figure is the total material cost of the metal coating and the
cost of processing, and does not include the cost of the carbon steel member being
galvanized/metallized.

 Metallizing is defined as the application of very thin metallic coatings for either active
corrosion protection (zinc or aluminum anodes) or as a protective layer (stainless steels
and alloys). Application can be by flame spraying or electroplating. Other advanced
processes such as plasma arc spraying can be used for exotic refractory metals for very
demanding applications, but most of the advanced processes are not used for corrosion
control. The metallizing anode market ranges from $5 million to $10 million annually,
and is also growing due to the recognition by government agencies that life-cycle costs
are significant if corrosion mitigation is not specified from the start

Electroless Plating

Electroless nickel (EN) plating is a chemical reduction process which depends upon the catalytic
reduction process of nickel ions in an aqueous solution (containing a chemical reducing agent)
and the subsequent deposition of nickel metal without the use of electrical energy. Due to its
exceptional corrosion resistance and high hardness, the process finds wide application on items
such as valves, pump parts etc., to enhance the life of components exposed to severe conditions
of service ,particularly in the oil field and marine sector. With correct pretreatment sequence and
accurate process control , good adhesion and excellent service performance can be obtained from
EN deposited on a multitude of metallic and non-metallic substra6tes.

In the EN plating process, the driving force for the reduction of nickel metal ions and their
deposition is supplied by a chemical reducing agent in solution. This driving potential is
essentially constant at all points of the surface of the component, provided the agitation is
sufficient to ensure a uniform concentration of metal ions and reducing agents. Electroless
deposits are therefore very uniform in thickness all over the part's shape and size. This process
offers distinct advantages when plating irregularly shaped objects, holes, recesses, internal
surfaces, valves or threaded parts. Distinct advantages of EN plating are:

 Uniformity of the deposits, even on complex shapes.

 Deposits are often less porous and thus provide better barrier corrosion protection to steel
substrates, much superior to that of electroplated nickel and hard chrome

 The deposits cause about 1/5th as much hydrogen absorption as electrolytic nickel and
about 1/10th as much hard chrome.
  Deposits can be plated with zero or compressive stress.

 Deposits have inherent lubricity and non-galling characteristics, unlike electrolytic

nickel.

 Deposits have good wetability for oils

 In general low phosphorus and especially electroless nickel boron are considered
solderable. Mid and high phosphorus EN's are far worse for solderability

 Deposits are much harder with as-plated microhardness of 450 - 600 VPN which can be
increased to 1000-1100 VHN by a suitable heat-treatment

The versatility of electroless nickel plating is demonstrated by the wide range of coatings
possible. The following are important types of coatings industrially available (reference):

 Low Phosphorous (Hard)

A unique bath providing an as-plated deposit hardness of up to 60 Rockwell This bath provides a
deposit nearly as hard as Hard Chrome, with the advantage of a uniform thickness inside
complex configurations, as well as outside. The deposit is so uniform that grinding after plating
is eliminated. Low Phosphorous Electroless Nickel offers excellent resistance to alkaline
corrosive environments.

 Medium Phosphorous (Bright High Speed)

This is a workhorse electroless nickel. It has proven itself over the years. Steel parts plated with
Medium Phosphorous electroless nickel will in many cases perform like stainless steel.
Electroless nickel will not build up on edges or ends, and it plates inside and out giving uniform
total coverage. With heat treatment, medium phosphorous electroless nickel can be hardened
from 45 Rockwell C to as high as 68 Rockwell C.

 High Phosphorous

This finish provides maximum corrosion resistance. High Phosphorous electroless nickel is
standard in industries that require resistance to strongly acidic corrosive environments like oil
drilling and coal mining. High Phosphorous electroless nickel has a low degree of solderability.
It will remain solderable for only a brief period of time after plating. This makes it a desirable
finish for electronics parts such as connector housings and semiconductor packaging.

 Electroless Nickel/Teflon Composite

Teflon adds to the already slick surface of the electroless nickel, yielding a very low friction
surface. This product is a relatively new one. It consists of microscopic beads of Teflon co-
deposited up to 20% with the electroless nickel. This finish can be the solution to sticking,
galling or drag problems with moving parts, or heated seal surfaces. In some cases, liquid
lubricants can be eliminated with the use of Nickel/Teflon plating.

 Electroless Nickel on Zinc Die Cast

Electroless nickel can be applied directly to zinc die cast without a copper layer. This has many
applications where corrosion resistance and resistance to chipping and flaking is necessary

The selection of a specific grade of EN-plating is done in accordance with the nature of
application, where a high hardness and low coefficient of friction is desired, low phosphorous
EN is preferred (1-3%P). For general applications where a bright finish is required and the
operating conditions are not very corrosive, medium phosphorous (6-8% P) EN is used e.g..
Computer printer rollers, machine components, plastic molding dies etc. When the conditions of
use for an EN plated components are severely corrosive, a high phosphorous EN (12-13% P) is
usually selected. The high phosphorous EN is amorphous in nature and is compressively stressed
unlike the low and medium phosphorous EN which are Crystalline and tensile stressed. Proper
process sequence and maintaining the correct operating parameters helps ensure a virtually non
porous deposit of high phosphorous ENP which finds wide application in areas such as valve
components, aerospace industry, oil & gas and chemical industries etc.

Physical Properties

 Surface Hardness: As plated 48-50 RC. After Heat Treatment (400°C, 1 hr) 62-63 RC

 Melting Point :- 890°C

 Density :- 7.85-7.95 gm/cm qb.

 Coefficient of friction :- EN Vs STEEL 0.3

 Coefficient of Thermal Expansion :- 0.13 microns /°c

Specifications and Testing

ASTM specifications are generally followed in evaluating EN plated components some of the
relevant tests are as follows

1. Hardness: The Hardness may be determined on a Microhardness Tester using a 100 gm

load as per ASST. B-578

2. Thickness: The microscopic examination of the cross section of an article is tested in

accordance with ASTM B-478. The ENplating thickness will vary from 5-125 microns
depending upon the service conditions.

3. Corrosion Resistance: A 5% neutral salt spray test is carried out as per ASTM B-117 to
determine the corrosion resistance of plated items. This is most important test in
 evaluating EN plated samples. The Corrosive conditions to which EN Plated components
are exposed, can be classified as mild, moderate and severe. The bath used for EN
Plating, varies accordingly to obtain alloy compositions varying from low to high
phosphorous content. Generally a high corrosion resistance requires a high phosphorous
content (10-12% ) and the relevant test to evaluate the performance of plated samples is
the 5% Neutral salt spray test in accordance with ASTM B-117. With a proper operating
procedure, high phosphorous deposits will show no rust spots, even after 1000 hrs of salt
spray exposure for a plating thickness of 40-50 microns.

4. Adhesion: Several tests such as Bend test, Quench test, Ring shear test etc. Are carried
our to determine the adhesion of EN-plating to the base metal in accordance with ASTM-
B-571.

Areas of Application

Due to its unique properties of excellent corrosion resistance, combined with a high wear
resistance and uniformity of coating, EN finds extensive applications in a number of fields. Some
of the prominent areas of application are:

1. Oil & Gas: Valve components, such as Balls, Gates, Plugs etc. And other components
such as pumps, pipe fittings, packers, barrels etc.

2. Chemical Processing: Heat Exchangers, Filter Units, pump housing and impellers,
mixing blades etc.

3. Plastics: Molds and dies for injecting and low and blow molding of plastics components,
extruders, machine parts rollers etc.

4. Textile: Printing cylinders, machine parts, spinneret's, threaded guides etc.

5. Automotive: Shock Absorbers, heat sinks, gears, cylinders, brake pistons etc.

6. Aviation & Aerospace: Satellite and rocket components, rams pistons, valve
components etc.

7. Food & pharmaceutical: Capsule machinery dies, chocolates molds, food processing
machinery components etc.