Industrial Materials and Processes

Fulgar, Jean Kathleen

Garingo, Abegail
Lim, Gobert
Mojica, Jamie Christine
Pajuelas, Norielyn
Quinto, Jonah Mae
Villarde, Edlene

August 20, 2016

WHAT IS CORROSION
Corrosion is the deterioration of materials by chemical interaction with their environment.
The term corrosion is sometimes also applied to the degradation of plastics, concrete and wood,
but generally refers to metals. The most widely used metal is iron (usually as steel) and the
following discussion is mainly related to its corrosion.

THE CONSEQUENCES OF CORROSION

The consequences of corrosion are many and varied and the effects of these on the safe, reliable
and efficient operation of equipment o rstructures are often more serious than the simple loss of a
mass of metal. Failures of various kinds and the need for expensive replacements may occur
even though the amount of metal destroyed is quite small. Some of the major harmful effects of
corrosion can be summarized as follows:
1. Reduction of metal thickness leading to loss of mechanical strength and structural failure or
breakdown. When the metal is lost in localized zones so as to give a crack-like structure, very
considerable weakening may result from quite a small amount of metal loss.
2. Hazards or injuries to people arising from structural failure or breakdown (e.g. bridges, cars,
aircraft).
3. Loss of time in availability of profile-making industrial equipment.
4. Reduced value of goods due to deterioration of appearance.
5. Contamination of fluids in vessels and pipes (e.g. beer goes cloudy when small quantities of
heavy metals are released by corrosion).
6. Perforation of vessels and pipes allowing escape of their contents and possible harm to the
surroundings. For example a leaky domestic radiator can cause expensive damage to carpets and
decorations, while corrosive sea water may enter the boilers of a power station if the condenser
tubes perforate.
7. Loss of technically important surface properties of a metallic component. These could include
frictional and bearing properties, ease of fluid flow over a pipe surface, electrical conductivity of
contacts, surface reflectivity or heat transfer across a surface.
8. Mechanical damage to valves, pumps, etc, or blockage of pipes by solid corrosion products.
9. Added complexity and expense of equipment which needs to be designed to withstand a
certain amount of corrosion, and to allow corroded components to be conveniently replaced.

CHEMISTRY OF CORROSION
Common structural metals are obtained from their ores or naturally-occurring compounds by the
expenditure of large amounts of energy. These metals can therefore be regarded as being in a
metastable state and will tend to lose their energy by reverting to compounds more or less similar
to their original states. Since most metallic compounds, and especially corrosion products, have
little mechanical strength a severely corroded piece of metal is quite useless for its original
purpose.
Virtually all corrosion reactions are electrochemical in nature, at anodic sites on the surface the
iron goes into solution as ferrous ions, this constituting the anodic reaction. As iron atoms
undergo oxidation to ions they release electrons whose negative charge would quickly build up
in the metal and prevent further anodic reaction, or corrosion. Thus this dissolution will only
continue if the electrons released can pass to a site on the metal surface where a cathodic reaction
is possible. At a cathodic site the electrons react with some reducible component of the
electrolyte and are themselves removed from the metal. The rates of the anodic and cathodic
reactions must be equivalent according to Faradays Laws, being determined by the total flow of
electrons from anodes to cathodes which is called the corrosion current, Icor.
Since the corrosion current must also flow through the electrolyte byionic conduction the
conductivity of the electrolyte will influence the way in which corrosion cells operate. The
corroding piece of metal is described as a mixed electrode since simultaneous anodic and
cathodic reactions are proceeding on its surface. The mixed electrode is a complete
electrochemical cell on one metal surface.
The most common and important electrochemical reactions in the corrosion of iron are thus
(2 Fe Fe) corrosion ( reaction Anodic2+ +(1) 3 2 H e 2 H 2)
simplified ( reactions Cathodic)
++(2a) or + + OH 2 e 2 O O H 2 212(2b)
Reaction 2a is most common in acids and in the pH range 6.5 8.5 the most important reaction
is oxygen reduction 2b. In this latter case corrosion is usually accompanied by the formation of
solid corrosion debris from the reaction between the anodic and cathodic products. hydroxide ) II
( iron , ) OH ( Fe OH 2 Fe 22 + +
Pure iron (II) hydroxide is white but the material initially produced by corrosion is normally a
greenish colour due to partial oxidation in air. oxide ) III ( iron hydrated , )
OH ( Fe 2 O O H ) OH ( Fe 23 2 212 2++

Further hydration and oxidation reactions can occur and the reddish rust that eventually forms is
a complex mixture whose exact constitution will depend on other trace elements which are
present. Because the rust is precipitated as a result of secondary reactions it is porous and
absorbent and tends to act as a sort of harmful poultice which encourages further corrosion.
For other metals or different environments different types of anodic and cathodic reactions may
occur. If solid corrosion products are produced directly on the surface as the first result of anodic
oxidation these may provide a highly protective surface film which retards further corrosion, the
surface is then said to be passive. An example of such a process would be the production of an
oxide film on iron in water, a reaction which is encouraged by oxidizing conditions or elevated
temperatures.
6 H 6 O Fe O H 3 Fe 23 2 2 + + ++

Corrosion prevention techniques can be generally classified

into 6 groups:
1. Environmental Modifications
2. Metal Selection and Surface Conditions
3. Cathodic Protection
4. Corrosion Inhibitors
5. Coating
6. Plating

Environmental Modification:
Corrosion is caused through chemical interactions between metal and gases in the surrounding
environment. By removing the metal from, or changing, the type of environment, metal
deterioration can be immediately reduced.
This may be as simple as limiting contact with rain or seawater by storing metal materials
indoors, or could be in the form of direct manipulation of the environmental affecting the metal.
Methods to reduce the sulfur, chloride or oxygen content in the surrounding environment can
limit the speed of metal corrosion.
For example, feed water for water boilers can be treated with softeners or other chemical media
to adjust the hardness, alkalinity or oxygen content in order to reduce corrosion on the interior of
the unit.

Metal Selection and Surface Conditions:

No metal is immune to corrosion in all environments, but through monitoring and understanding
the environmental conditions that are the cause of corrosion, changes to the type of metal being
used can also lead to significant reductions in corrosion.
Metal corrosion resistance data can be used in combination with information on the
environmental conditions to make decisions regarding the suitability of each metal.

The development of new alloys, designed to protect against corrosion in specific environments
are constantly under production. Hastelloy nickel alloys, Nirostasteels and
Timetal titanium alloys are all examples of alloys designed for corrosion prevention.
Monitoring of surface conditions is also critical in protecting against metal deterioration from
corrosion. Cracks, crevices or asperous surfaces, whether a result of operational requirements,
wear and tear or manufacturing flaws, all can result in greater rates of corrosion.
Proper monitoring and the elimination of unnecessarily vulnerable surface conditions, along with
taking steps to ensure that systems are designed to avoid reactive metal combinations and that
corrosive agents are not used in the cleaning or maintenance of metal parts are all also part of
effective corrosion reduction program.

Cathodic Protection:
Galvanic corrosion occurs when two different metals are situated together in a
corrosive electrolyte. This common problem for metals submerged together in seawater, but can
also occur when two dissimilar metals are immersed in close proximity in moist soils. For these
reasons, galvanic corrosion often attacks ship hulls, offshore rigs and oil and gas pipelines.
Cathodic protection works by converting unwanted anodic (active) sites on a metal's surface to
cathodic (passive) sites through the application of an opposing current.
This opposing current supplies free electrons and forces local anodes to be polarized to the
potential of the local cathodes.
Cathodic protection can take two forms. The first is the introduction of galvanic anodes.
This method, known as a sacrificial system, uses metal anodes, introduced to the electrolytic
environment, to sacrifice themselves (corrode) in order to protect the cathode.
While the metal needing protection can vary, sacrificial anodes are generally made
of zinc, aluminum or magnesium, metals that have the most negative electro-potential.
The galvanic series provides a comparison of the different electro-potential - or nobility - of
metals and alloys.

In a sacrificial system, metallic ions move from the anode to the cathode, which leads the anode
to corrode more quickly than it otherwise would. As a result, the anode must regularly be
replaced.
A second method of cathodic protection is referred to as impressed current protection.
This method, which is often used to protect buried pipelines and ship hulls, requires an
alternative source of direct electrical current to be supplied to the electrolyte.
The negative terminal of the current source is connected to the metal, while the positive terminal
is attached to an auxiliary anode, which is added to complete the electrical circuit.
Unlike a galvanic (sacrificial) anode system, in an impressed current protection system, the
auxiliary anode is not sacrificed.

Cathodic Protection

Figure 2: Iron Protected With Sacrificial Anode mainly iron, from corrosion. A sacrificial
anode is a substance that is easier to oxidize then the structure being protected, typically
it is a relatively small and easy to replace piece of metal. From the standard electric
potentials below:
Fe(s) <-> Fe2+ + 2e- + 0.44

Zn(s) <-> Zn2+ + 2e- + 0.76

Mg(s) <-> Mg2+ + 2e- + 2.37
Both magnesium (Mg) and zinc (Zn) have higher potentials so they will be oxidized
before iron if they are connected in a system. When either magnesium or zinc anodes are
connected to an iron structure electrons will move from the sacrificial anode through the
iron structure and to the reduction reaction site. This causes the iron structure to retain its
electrons and not corrode until the anode has been used up.
Sacrificial anodes are used when the pipeline is temporary or where there is not access to
a power supply.

Impressed Current Cathodic Protection (ICCP): This form of corrosion protection is

applied by connecting the negative terminal of a DC power source to the iron structure
and the positive terminal to an anode. Because the driving voltage is provided from a
DC source and not electric potentials the anode does not need to oxidize and an inert
anode can be used. There are 3 main advantages to using ICCP, one being that the DC
power sources can provide much higher driving voltages then sacrificial anodes (100 to

10,000 times higher) and can protect larger areas. The second main advantage is that the
anodes that are used, such as graphite, are inert and dont need to be continuously
replaced. The final advantage is the degree of control over the electron transfer that
ICCP has, the current can be increased or decreased as need be.
ICCP is what is typically found on all pipelines as it does not have to continuously

Corrosion Inhibitors:
Corrosion inhibitors are chemicals that react with the metal's surface or the environmental gases
causing corrosion, thereby, interrupting the chemical reaction that causes corrosion.
Inhibitors can work by adsorbing themselves on the metal's surface and forming a protective
film. These chemicals can be applied as a solution or as a protective coating via dispersion
techniques.
The inhibitors process of slowing corrosion depends upon:

Changing the anodic or cathodic polarization behavior

Decreasing the diffusion of ions to the metal's surface

Increasing the electrical resistance of the metal's surface

Major end-use industries for corrosion inhibitors are petroleum refining, oil and gas exploration,
chemical production and water treatment facilities.
The benefit of corrosion inhibitors is that they can be applied in-situ to metals as a corrective
action to counter unexpected corrosion.
Corrosion Inhibitors
Corrosion inhibitors offer corrosion protection that is similar to coatings as they act as a
barrier between the oxidizing agents and the metal surface. The inhibitor adsorbs onto the
steel surface and slows down or eliminates one or more of the electrochemical reactions
by blocking the reaction site. The degree of protection that a corrosion inhibiter provides

is heavily dependent on the properties of the inhibitor, the properties of the steel and the
fraction of the steel surface that is blocked by the inhibitor.
Liquid phase inhibitors (LPIs): LPIs are in wide scale use to combat CO2 corrosion in
pipelines. The inhibitor is that is injected into the pipeline is transported in low
concentrations and adsorbs onto the surface of the steel. Because the inhibitor is in the
liquid phase only the interior of the pipeline needs to be in contact with the liquid either
continuously or semi-continuously. One of the main benefits in using inhibitors to protect
from CO2 corrosion is that it can continuously be added to the flow to provide
continuous protection.

Volatile corrosion inhibitors (VCIs): VCIs are similar to liquid phase inhibitors in that
they are present in low concentrations in the pipeline. Because they are a volatile
compound they can easily enter the vapour phase if one is present. VCIs can absorb onto
the steel directly from the vapour phase and can penetrate into complex shapes and
imperfections better than LPIs. Any condensate that may form on the inside of the pipe
may contain water and CO2 which will contribute to corrosion in the pipe. If VCIs are
present in the vapour phase they will also condense and provide a protective film.
The volatility of the inhibitor is dependent on the vapour pressure of the compound. For
the prevention of CO2 corrosion on steel, amines are used as the VCI. The vapour
pressure of amines is ideal so that the VCI will be present in both phases and provide
ideal coverage for the pipeline.

Coatings:

Paints and other organic coatings are used to protect metals from the degradative effect of
environmental gases.
Coatings are grouped by the type of polymer employed. Common organic coatings include:

Alykd and epoxy ester coatings that, when air dried, promote cross-link oxidation

Two-part urethane coatings

Both acrylic and epoxy polymer radiation curable coatings

Vinyl, acrylic or styrene polymer combination latex coatings

Water soluble coatings

High-solid coatings

Powder coatings

Plating:
Metallic coatings, or plating, can be applied to inhibit corrosion as well as provide aesthetic,
decorative finishes.
There are four common types of metallic coatings:
1. Electroplating: A thin layer of metal - often nickel, tin or chromium - is deposited on the
substrate metal (generally steel) in an electrolytic bath. The electrolyte usually consists of
a water solution containing salts of the metal to be deposited.

2. Mechanical plating: Metal powder can be cold welded to a substrate metal by tumbling
the part, along with the powder and glass beads, in a treated aqueous solution.
Mechanical plating is often used to apply zinc or cadmium to small metal parts

3. Electroless: A coating metal, such as cobalt or nickel, is deposited on the substrate metal
using a chemical reaction in this non-electric plating method.

4. Hot dipping: When immersed in a molten bath of the protective, coating metal a thin
layer adheres to the substrate metal.

Coatings

Coatings provide physical barriers that do not allow corrosive materials to come in
contact with the structure that is being protected. Mainly, coatings are used on the
exterior of pipelines to protect from external factors and are not used to directly protect
the pipeline from CO2 corrosion. The most common type of coatings are painting and
platting which both provide effective corrosion protection and aesthetic appearance.
Painting: Painting is an effective way to protect pipelines from external environmental
factors. Although when looking at CO2 corrosion on the interior of the pipeline, it is not
ideal because painting the inside of a pipeline is impractical. The paint will breakdown
over time, either through chemical reactions with the flowing fluid or the erosion due to
turbulent or transient flow. Once the coating has broken down it leaves unprotected
sections of the pipe when fluid induced localized corrosion occurs.
Plating: Plating involves using electric currents to coat a metal with a thin layer of
another metal that acts as a protective barrier. Plating an entire pipeline is very
uncommon as it is expensive; however, it can be done when dealing with high pressures
and high amounts of H2S and CO2. One draw back of plating is if the plating fails in a
small section (either an imperfection or a scratch) then highly localized corrosion occurs.
Another factor to consider is if the plating is more noble than the pipeline (for example,
chromium on steel), the steel will act as a sacrificial anode for the chromium. This causes
the exposed area to corrode much more rapidly than an un-plated surface would.

Epoxy Coated Reinforcing Bars

Epoxy provides a barrier coating to the steel and, thereby, prevents the chlorides from breaking down the
passive layer on the steel providing a longer service life. While many structures with epoxy-coated steel
have performed well, some have not. The latter cases have been attributed either to flaws in the coating,
most likely due to defects introduced during construction, or to absorption of moisture by the epoxy
leading to swelling and debonding from the steel [45, 46]. It is generally concluded that good quality
epoxy coatings will increase the time to initiate corrosion but, once initiated, the corrosion rate will be
about the same as that of uncoated black steel.

Stainless steel reinforcing bars

With increasing service life requirements, stainless steel is being regarded as a viable alternative
reinforcement despite its higher cost. The most common grades of stainless steel for reinforcement are
316LN and 2205, both of which have excellent corrosion resistance [47, 48] and are commercially
available. They should provide service lives well in excess of 100 years. Research shows that grade 304 is
less corrosion resistant than the other two grades [49] but, in fact has the longest successful field record of

any stainless steel [50]. The cost of the stainless steels is more than five times that of black steel [51] but,
on a life cycle cost basis, they are considered to be cost-effective [52].
Corrosion resistant reinforcing bars MMFX and 2201LDX
In order to provide better corrosion resistance than black steel but at lower cost than the traditional
stainless steels, efforts have been made in recent years to develop corrosion resistant alloys for
reinforcement. Three examples of these steels are (i) a low carbon, low chromium micro composite
steel designated as MMFX-2 (ASTM A615 Grade 75) [53],
(ii) a 1.5% Ni 21% Cr alloy designated 2101LDX (ASTM A955-98) [51], and (iii) a 3% Ni, 12% Cr alloy
designated 3Cr12 [53]. In macro cell corrosion tests [54], the corrosion initiation times for these alloys
were measured to be 2, 7 and 1.6 times that of black steel, whereas the 304 and 316LN grades had
initiation times in excess of 12 times that of the black steel (i.e. they had not begun to corrode during the
period of the research). The corrosion rates of the MMFX and 2102LDX after initiation were less than
half of that exhibited by the black steel. Their cost is between 2 and 4 times that of black steel, whereas
the cost of the stainless steels is more than five times that of black steel [55].
Other investigators [56] have concluded that high performance alloys outperformed black steel from a
corrosion resistance standpoint. Unlike the various grades of black steel however, a relatively wide range
of corrosion performance was apparent for the high performance counterparts depending on the alloy and
surface condition.

Galvanized steel reinforcing bars

Galvanized steel reinforcement has been used in reinforced
concrete structures since 1930s [57]. The advantages of
hot-dipped galvanizing are two-fold: unlike most other
forms of coatings, a metallurgical bond is formed between
the steel and the zinc which means that the coating is not
susceptible to flaking or other forms of separation from the
substrate. Secondly, zinc not only forms a barrier coating
but acts as a sacrificial anode. Thus, any scratches or other
flaws in the coating are not critical and do not lead to
active corrosion of the underlying steel. Zinc has the
advantage over black steel that it can tolerate more
chlorides (approx 2.5 times [58-60] and lower pH levels
[pH~8] before significant active corrosion is initiated.
Thus, it would provide better protection than black steel to
both chloride-induced and carbonation-induced corrosion.
The galvanized layer has the disadvantage that it corrodes very rapidly in the wet cement but this reaction
rate ceases once the concrete hardens [61, 62]. While chromating the galvanized bars has been performed
to minimize this initial corrosion, the use of chromates is not recommended because of adverse health
effects of the hexavalent chromate ions. However, recent research has indicated the effect of chromating

is minimal at best [62]. Because of its passivation in neutral solutions and its sacrificial anode role when
in contact with steel, galvanized steel is ideally suited for parts which are to be partially embedded in
concrete and partially exposed to the atmosphere.

Non-metallic reinforcement
The carbon-fiber reinforcements currently being marketed [63] do not suffer from corrosion and will not
be discussed here. The long term performance of these materials in concrete has not yet been evaluated.
Whether the epoxy matrix for these bars will suffer the moisture absorption that was observed in epoxy
coatings is not yet known.

The Corrosion Behavior of Other Metals in Concrete

Aluminum and its alloys
Aluminum develops a passivating layer on its surface at pH 4-9 [6] which protects it from further
corrosion. However, the passive layer is unstable in alkaline environments and aluminum reacts with
sodium and potassium hydroxides in concrete, a reaction which is accompanied by the evolution of
hydrogen gas. This reaction occurs at high rates in wet concrete causing plastic concrete to develop a very
porous structure as it hardens. This may affect the bond between aluminum and concrete, as well as,
increase the ingress of chloride ions into concrete which exacerbates the corrosion of aluminum. The use
of chloride admixtures also greatly increases aluminum corrosion and spalling. The corrosion products of
aluminum are extremely expansive and cause cracking and spalling of the surrounding concrete [64, 65].
Aluminum elements should never be embedded in concrete exposed to moist service environments,
unless the aluminum is prevented from direct contact through use of a protective barrier.

Lead
Although lead is deemed to have superior corrosion properties to those of steel and aluminium under
atmospheric conditions, it reacts with calcium hydroxide in concrete to form soluble lead oxides and
hydroxides, which do not protect the metal from further corrosion. As with aluminum, the reaction occurs
at high rates in wet concrete which decrease as concrete hardens. If lead is to be placed in wet concrete, it
should be protected using bituminous or plastic coatings [64, 65].

Copper and its alloys

Copper and its alloys do not corrode in non-chloride contaminated concrete provided it does not contain
ammonia and nitrates, which can induce stress corrosion cracking in the metal. The copper oxide formed
in alkaline environments such as concrete is not soluble and, hence, forms a protective layer that limits
further corrosion.
However, the presence of chlorides in concrete perforates copper [64, 65]. Macdonald et al. [14] tested
copper clad reinforcement and found it to have significantly higher resistance to chloride induced
corrosion than did black steel.

Service Life of Reinforced Concrete Exposed to

Chlorides
The service life of black steel reinforcement in OPC concrete is often depicted as consisting of two
phases: an incubation period during which chlorides or carbonation penetrates the cover, and a
propagation period where active corrosion causes degradation of the concrete.

Corrosion Monitoring Techniques

One of the major problems associated with reinforcement corrosion is that its initiation and early stages of
propagation cannot be detected visibly. Yet early detection of corrosion in a reinforced concrete structures
can provide the opportunity to schedule appropriate maintenance procedures, thereby ensuring the safety
of the structure. If corrosion remains undetected until cracking and spalling occur, then the costs of repair
are significantly higher because all of the concrete cover and much of the reinforcement must be replaced.
Moreover, patch repair at this time can enhance active corrosion in the surrounding original reinforcement
and lead to a continuous cycle of repairs.
The most commonly used techniques for evaluating the condition of embedded reinforcement are based
on the electrochemical nature of the process. The electrons released by the iron as it corrodes (Equation 1)
and consumed by the dissolved oxygen (Equation 2) constitute a current, illustrated in Figure 3, which
can be indirectly measured. This current, representing dissolution of one iron atom for each two electrons
in the current, can be converted to thickness of steel dissolved by the equation: 1mA/m2= 1.16 mm/year =
0.0456 mils/year (mpy) (Eq. 3)The currently available electrochemical monitoring techniques are
described below. Unfortunately only a few of these can be readily used in the field.
Half-cell potential mapping
Half-cell potential measurements are the most widely used method of detection of corrosion of steel
reinforcement in concrete. The method was introduced in the 1970s by Richard F. Stratfull in North
America [74, 75] and by the Danish Corrosion Centre in Europe [75-77] and was approved in 1980 as a
standard by ASTM [78]. ASTM C 876 involves measuring the electrochemical potential of the steel
reinforcement with respect to a copper/copper sulfate reference electrode by connecting one wire of a
high impedance voltmeter to the reinforcement and the other to the reference electrode placed on the
surface of the concrete. The voltage can provide an indication of the probability of active corrosion of the
steel. The recommended ASTM interpretation of the measurements is as follows:
Half-cell potential reading vs. Cu/CuSO4 Corrosion activity
More positive than -200 mV 90% probability of no corrosion
Between -200 and -350 mV An increased probability of corrosion
More negative than -350 mV 90% probability of corrosion

Probability of Corrosion of Carbon Steel According to Half-Cell Potential

Reading
It is important to note that the interpretations are of probabilities of corrosion only and that there are other
possible causes of high negative potentials. For example, in deaerated concrete, such as that submerged in
deep water, potentials as low as -700 mV are normal despite the fact that the steel remains passive. It
should also be noted that half-cell potentials give no indication of the rate of corrosion, nor of how long
the steel has been corroding.
Linear Polarization Resistance (LPR)
When a very small electrical potential (of the order of 10 mV) is applied to the corroding steel, the
relationship between potential and current is linear. The polarization resistance,
Rp, is the ratio of the applied potential to resulting current and is inversely proportional to the corrosion
rate [79, 80]. In order to calculate a corrosion rate with the LPR technique, the following fundamental
assumptions must be made [5]:
- uniform corrosion damage;
- the rate controlling step in corrosion is activation polarization (i.e. the ease of stripping electrons from
the iron);
- there is a single anodic and a single cathodic reaction;

Corrosion
- the proportionality constant between corrosion rate and Rp must be known;
- the electrical resistance of the solution (i.e. the concrete) is negligible;
- the half-cell potential is stable.
In fact, of these assumptions, only the third one is applicable to the case of chloride induced corrosion of
embedded reinforcement. Despite this, the LPR technique has become increasingly popular for measuring
corrosion in the field because: (i) it is a nondestructive technique;
(i) it is simple to apply and (iii) it usually needs only a few minutes for corrosion rate determination [81].
Consequently, an increasing number of commercial instruments are available for field measurements of
LPR.
Measurements are performed by applying a potential in the range of 10 to 20 mV about the Ecorr, either
as a constant pulse (potentiostatic), or a potential sweep
(potentiodynamic), and measuring the current response.
Alternatively, a current pulse (galvanostatic) or a current sweep (galvanodynamic) can be applied, and
potential response is measured. The RP and, in turn, the corrosion rate is calculated by the instrument.

In addition to the assumptions mentioned above, the major limitation of these techniques is that it is
impossible to know the area of steel which is being polarized by the applied potential, or the area which is
actively corroding. Therefore, the corrosion is generally considered to be uniform over the polarized area
and the measured corrosion current is divided by a guesstimated polarized area to give an average
corrosion rate. An additional limitation is that this is an instantaneous corrosion rate and (a) gives no
indication of how long corrosion has been going on or (b) how the corrosion rate varies with time and
ambient conditions.
An example of how much corrosion rates vary is given in Figure 11 together with the corresponding
temperature and relative humidity variations inside the concrete over the same time period. It should be
noted corrosion rate increases or decrease with increasing or decreasing temperature, as expected. The
relative humidity, on the other hand, remains approximately constant, at ~100%, over this period, despite
significant changes in the external temperature and relative humidity. This illustrates that the concrete is
not dried out at all at depths of approximately 25 mm, and that only the surface layers are affected by
drying. Attempts to overcome the uncertainty in the polarized area have resulted in the development of
the guard ring. The objective of the guard ring is to concentrate the polarization to within a specified
length of the steel reinforcement. Guard ring electrodes have been incorporated in several commercial
corrosion measurement instruments [82, 83]. Figure 11. (a) Corrosion rate of steel, (b) internal
temperature and (c) internal relative humidity variations in OPC concrete [41].Studies have shown,
however, that all of instruments have some limitations [84-86] and that the use of a guard ring does not
solve all of the deficiencies of the technique..Cyclic potentiodynamic polarization or Cyclic polarization
is relatively non-destructive technique that provides the corrosion rate, corrosion potential and
susceptibility to pitting corrosion of the metal in the test environment, as well as giving information about
the expected behavior of the steel should its potential be changed by, for example, exposure to stray
currents, coupling with other metals or the surrounding concrete becoming anaerobic. Like most
electrochemical techniques, cyclic polarization is carried out with three electrodes: a working electrode
(the reinforcing steel), a
0
20
40
60
80
100
120
40 60 80 100 120140160180200220 240 260 Time (days after casting)
Relative Humidity(%)
-25

-20
-15
-10
-5
0
5
10
15
20
25
30
35
40
40 60 80 100 120 140 160 180 200 220 240 260 Time(days after casting)
Temperature (C)
0
0.005
0.01
0.015
0.02
0.025
0.03
40 60 80 100 120 140 160 180 200 220 240 260 Time (days after casting)

Corrosion
The potential of the specimen is changed continuously or in steps, while the resulting current is
monitored. From a plot of the applied potential versus the logarithm of the resulting current density, the

condition of the steel in the present environmental, as well as its potential behavior under other
conditions, can be assessed. Cyclic polarization is most useful in the laboratory, for example, to evaluate
the behavior of steel in new concrete mixes or the behavior of alternative reinforcing materials in normal
concrete. While such tests have been successfully performed in the field by the authors, they suffer the
same limitation of LPR that of knowing the polarized area of the steel, as well as taking a longer time to
perform.Electrochemical Impedance Spectroscopy (EIS)
Analyzing the response of corroding electrodes to small-amplitude alternating potential signals of widely
varying frequency is the basis of EIS [81]. EIS has become popular as a tool of corrosion measurement
and monitoring applications for which traditional DC techniques have been unsuitable. It has been used
extensively for coated and painted materials to detect the impact of holidays (flaws) in the coating. Thus it
is a useful technique for evaluating epoxy-coated reinforcement [87]. It has also been employed to
evaluate the effectiveness of cathodic protection [86] and corrosion inhibitors [88] as well as chloride
diffusivity in concrete [89] and electrical resistance of concrete. Most of these studies have been carried
out in the laboratory and, based on the authors experience, this technique is unsuitable for field
measurements because the measurements take too long and because the system is susceptible to electrical
interference.Prevention and Protection Methods

Cathodic Protection (CP)

The first example of cathodic protection applied to concrete structures was reported in 1957 [90] and
widespread use of the technique for protecting bridge decks contaminated by deicing salts began in 1973
in North America [91, 92].Cathodic protection is based on changing the potential of the steel to more
negative values. This potential change can be obtained by connecting an external anode to the steel and
impressing an electrical DC current through the reinforcement using a rectified power supply. Activated
titanium expanded mesh with a surface coating of titanium oxide is the most widely used anode in
practice. This external anode is mounted on the surface of concrete. The positive terminal of low voltage
DC current source is connected to the mesh and the negative terminal is connected to the steel bars. In
order to halt corrosion of the reinforcement completely, the potential would have to be lowered to values
more negative than ~ -1200 mV CSE (immunity region in Pourbaix diagram for iron) [6].However, at
those values, the cathodic reaction would result in hydrogen evolution which could cause hydrogen
embrittlement of any pre stressed steel in the structure. Consequently, the potential is carefully controlled
to a level (typically -1000 mV CSE) at which the corrosion is negligible but not actually stopped.
Alternatively, the process can rely on the galvanic effect and a less noble metal can be used as sacrificial
anodes. In this case, metals such as zinc and zinc-aluminium alloys, are applied to the concrete surface by
flame spray, as a mesh or sheet adhered via a conductive gel [93].CP must be applied for the remaining
lifetime of the structure and must be monitored regularly. For this purpose, the potential of the steel
should be monitored with respect to a reference electrode before and after disconnecting the system to
make sure that the system is depressing the potential from the open-circuit potential. The limits and
standard practices are outlined in [94]. Resistance of the concrete should be considered. Electrochemical
Chloride Extraction (ECE)The goal is to repel the (negatively charged) chloride ions from the
reinforcement and out of the surface of the concrete by applying a negative charge to the reinforcement,
as illustrated schematically in Figure 12. ECE is similar to CP but a higher current is applied for a short
period of time (a matter of weeks). During the treatment, any corrosion products are electrochemically
reduced at the reinforcing steel [95].ECE is being applied successfully in North America but the long term

effects of such treatment have not yet been evaluated.. Schematic illustration of the application of the
electrochemical chloride extraction treatment to a corroding reinforced concrete structure [95].
EXTERNAL ANODE, REINFORCING STEEL, CONCRETE, POWER SUPPLY
Reduction of Corrosion products
2HO +O +4e 4OH 2 (I) 2,(g) (aq) - -
H O+2e 2OH +H 2 (I) (aq) 2,(g) - -
Cations(e.g.,K ,Na, Ca ,Mg)
+ + 2+ 2+
Anions(e.g.,OH, Cl)
- -4 OH 2H O+O +4e- -(aq) 2 (I) 2,(g)
2HO 4H +O +4e 2 (I) (aq) 2,(g) + -2Cl Cl +2e- -(aq) 2,(g)

Corrosion
that the applied current can significantly alter the composition and morphology of the mortar at the
steel/mortar interface and the steel/concrete bond strength [96, 97]. ECE is best applied when the
chlorides are almost reaching the reinforcing steel but have not yet initiated active corrosion. It cannot
stop the damage if the process of deterioration is advanced. Therefore, the extraction treatment may be
considered an appropriate preventive method but, strictly speaking, not a rehabilitation method. Thus,
while the electrochemical extraction process is obviously successful in removing the chlorides, it should
be used with caution and practical limits of current density should be established to minimize the harmful
effects.

Inhibitors
Corrosion inhibitors are defined as chemical compounds that reduce the corrosion rate by affecting the
anodic or cathodic half-cell reactions or both. It should be noted that the materials which affect the
transportation mechanism of the aggressive species to the reinforcing steel bars are not considered
inhibitors. A corrosion inhibiting admixture to concrete can function by:
- Increasing the resistance of the passive film on the steel to breakdown by chlorides
- Creating a barrier film on the steel;
- Increasing the degree of chloride binding in the concrete;
- Scavenging the oxygen dissolved in the pore solution; and

- Blocking the ingress of oxygen.

Numerous compounds have been investigated in the laboratory as potential corrosion inhibiting
admixtures to concrete and the most widely used ones are summarized in The Most Widely used
Inhibitors for Applying in Steel Reinforced.
The efficiency of the inhibitors in steel reinforced concrete structures has not yet been proved and there
are many discussions in this area. Lack of understanding the mechanism, environmental and safety
aspects are some on the major limitations of using inhibitors in reinforced concrete structures properly
[99, 101]. Consequently, while calcium nitrite is used in many jurisdictions and is required in some, it is
not permitted in others. Corrosion inhibitors should conform to ASTM C 1582.

Non-chloride de-icing agents

Sodium chloride, calcium chloride and magnesium chloride have traditionally been used for snow and ice
removal operations. However, these de-icers cause durability problems in concrete structures,
Environmental concerns

Inhibitor Application Mechanism

Calcium nitrite Added to the mixing water of concrete. Due to the negative charge of nitride, it migrated
into the pit and enhances passivation by its oxidative properties
Calcium nitrate Added to the mixing water of concrete In the presence of corrosion products, nitrate is
reduced to nitrite. This reaction in alkaline environment is fast enough to provide required nitrite to
inhibit corrosion
Sodium monofluorophosphate (MFP) Added to the mix or applied to the surface. None of the studies on
MFP determined the mechanism by which MFP inhibits the corrosion of steel in concrete (anodic,
cathodic or mixed).
Hydroxyalkylamines Added to the mix or applied to the surface. Generally, is produced in a gas phase and
migrate relatively fast to the surface of concrete and reduces the corrosion rate. No detailed information
available regards to protection mechanism