School of Multidisciplinary Engineering
Center of Materials Engineering
Corrosion and deterioration of materials
Concrete Corrosion
Prepared by: Desalegn Shibesh
ID: GSR/9086/12
Submitted to: tesfay Refera (Ph. D.)
May /2020
Contents
Concrete Corrosion
Introduction
Enginering
properties of concrete
Chemistry of Portland Cement
Concrete Chemistry Hydration Reaction
Durability and Deterioration of Cement
Corrosion of Rienforcement (Rebar Corrosion)
Factor Affecting Corrosion
Effect of Permeability of Concrete
Construction Practice
Method of Corrosion Control of Reinforcing steel
Concrete Repair and Rehabilation
Electrochemical Methods of Evaluation of Rienforcement Corrosion
Concrete Corrosion
Introduction
Concrete
material is the most widely used construction material in
the world . It can be defined as the artificial stone produced when
cement (usually Portland cement) is mixed with fine aggregate
(sand), a coarse aggregate (gravel or crushed stones) and water.
in spite of the impressive performance of concrete in several
structures, the deterioration of concrete has assumed alarming
proportion in harsh climatic conditions, such as the sea-coastal areas
in Gulf countries
Introduction…
Aggregates
Aggregates used in normal construction comprise granular
materials, like limestone, dolomite, gravel, silica, etc
The salts in the aggregates, such as sulfates, chlorides and
carbonates of calcium, magnesium and sodium, contribute to
the corrosion of concrete
The aggregate size used includes both fine and coarse fractions.
The coarse fraction refers to particles greater than 4.75 mm and
fine fraction to particles smaller than 4.75 mm but larger than
75 micron meter. The aggregate makes up from 65-75% of
volume of concrete.
Introduction…
Admixtures
These are inorganic or organic substances that are added to the fresh
concrete before or during mixing to modify some properties, such as
their setting and hardening characteristics.
The most common mixtures are the air-entraining
type. They form a network of voids (0.001- 0.003 in diam) in the
cement phase of concrete.
Self-retarding admixtures increase the setting time for concrete,
whereas self-accelerating mixtures decrease the setting time.
Polymers are used for bonding and plasticizers for setting of
concrete. Over-dosing with admixture may create
problems
Introduction…
water to Cement Ratio
The compressive strength and density of concrete is
strongly influenced by the water-cement ratio. The most of
time the water-cement ratio is in the range of 0.4-0.5.
A low water-cement ratio is necessary for the production of
high strength cement.
Introduction…
Classification of Concrete
They are classified in three different categories:
• Low strength - Less than 20 MPa
• Medium strength - Between 20 and 40 MPa
• High strength - Greater than 40 MPa
Enginering properties of concrete
Densitty
The density of concrete is controlled by the water-cement ratio, air
contents and specific gravity of the aggregates used.
Porosity
The porosity include voids created by entrained air, aggregate and gel
pores (-18 A), and capillary pores in the hydrated cement paste .
The magnitude of porosity is directly affected by water- cement ratio,
the amount of entrained air and the nature of aggregates.
Enginering properties of concrete...
Compressive Strength
Concrete has a high compressive strength. The classification of concrete on the
basis of compressive strength has been shown earlier. The water-cement ratio has
an important bearing on the compressive strength of concrete.
Tensile Strength
This is one area of weakness of concrete. Concrete is strong in comprehensive
strength but is very weak in tensile strength. This inherent weakness of concrete
led to the idea of using steel as a reinforcement to increase its capability to carry
large tensile loads. The tensile strength of typical concrete does not exceed 2-4
MPa.
Drying Shrinkage
If concrete is exposed continuously to water, it exhibits insignificant expansion
over a period of several years. Concrete exposed to dry and wet conditions would,
however, be subjected to
loss of water causing it to contract and leading to its cracking due to development
of internal
stresses. The shrinkage caused by drying of water in concrete is called shrinkage.
Chemistry of Portland Cement
Cement
is generally termed as Portland cement. The production of cement involves heating a
mixture of CaO and Si02 (such as, limestone and clay) in a kiln (1350°C). Cement is the most
reactive ingredient in Portland cement concrete, the others, such as aggregates, are relatively
inert.
The major constituents of Portland cement shown above are not pure compounds. The four
major constituents make up about 93% by weight. All five types of cement contain the four
major constituents (C3S, C2S, C3A and C4AF) in different proportions.
the five major types of Portland cement are shown in Table:
Concrete Chemistry Hydration Reaction
The
chemistry of concrete primarily involves a study of hydration
products of concrete formed on addition of water.
The most important reactions occur with C2S (2CaOSi02) and C3S
(3CaOSi02). The rate
of hydration reaction is affected by temperature. Increased temperature
leads to an increased rate of hydration, but it leads to a decreased tensile
strength of concrete. The resulting hydration paste comprises
heterogeneous product.
The
paste can be described as a crystalline gel which is made of cement
gel, unhydrated cement, capillary pores containing water vapor, water and
air. The gel pores are very small in size and they are filled with water .
Durability and Deterioration of Cement
Concrete
is a building material of the twentieth century and has been extensively used
in temperature and harsh climatic conditions with success.
Concrete is a very durable material, and steel embedded in concrete functions as a
very effective reinforcement. Concrete provides an alkaline environment to steel and
minimizes the risk of corrosion of steel. Two conditions are essential for durability of
concrete:
(a) The concrete should be of high quality and should not undergo environmental
degradation.
(b) The reinforcing steel must not be allowed to corrode, by maintaining the
alkaline environment.
However, under certain environmental conditions, concrete may undergo degradation
and reinforcing steel may also corrode.
Durability and Deterioration of Cement...
Degradation of Concrete
Conditions which exist at the time of production of concrete and its exposure to an external
environment during its working life time, are two major factors which affect the durability of
concrete.
(a) Conditions Prevailing at the Time of Production:
• At higher temperatures in hot weather
• rapid rate of hydration reaction
• Rapid evaporation of mixing water
• In cold weather, the mixing water
(b) Environmental Factors Affecting the Durability of Hardened Concrete :
• Freeze-thaw cycling
• Drying shrinkage
• Carbonation shrinkage
• Humidity
• Sulfate attack
• Seawater
Corrosion of Rienforcement (Rebar Corrosion)...
Concrete, in general, provides protection to steel reinforcement because of the following
two reasons:
(a) Concrete provides a highly alkaline environment to steel reinforcement which
passivates the steel surface and, hence, prevents it from corrosion.
(b) Concrete prevents the ingress of corrosion species, like oxygen, chloride ions, carbon
dioxide and water, in low water-cement ratio concrete.
certain regions bestowed with high humidity, high temperature, persistently wet
conditions and presence of hygroscopic species, such as dust and salt particles in air cases
of failure of reinforced concrete structures.
it is essential to maintain a high quality of concrete and minimize the factors which lead to
its deterioration, such as quality of mixing water and aggregates, porosity, permeability,
freeze-thaw cycles and sulfates.
These factors coupled with inappropriate construction characteristics in harsh
environmental conditions lead to the onset of corrosion of the steel reinforcement
Corrosion of Rienforcement (Rebar Corrosion)...
The
formation of protective oxide layers and their breakdown is shown in Figures. The protective
oxide layers that developed are either Fe203 or Fe3C>4, both are stable in concrete.
The most stable layer in concrete is Fe203 written as y-FeOOH. It is formed by the interaction of
O2 with Fe(OH)2.
The
growth of a rust layer induces mechanical stresses in the concrete and leads to its deterioration.
Once corrosion initiates, controlling becomes extremely difficult unless detected in early stage.
Factor Affecting Corrosion
it is important to understand the contribution of important factors
which induce corrosion.
Loss of Passivation (Depassivation)
Two major factors destroy the passivation of steels in concrete:4
Ingress of Carbon Dioxide (Carbonation)
The carbon dioxide molecules that penetrate in the concrete react
with the solid calcium.
hydroxide gel, and with alkali and calcium ions in the pore
solution of the concrete causing a drastic
decrease in the alkalinity due to a fall in pH from 14.0 to about 8.0.
There are other secondary factors, such as depth of reinforcement
cover, moisture conditions, humidity, Solubility of CO2, Water-
cement ratio ,and temperature, which also influence carbonation.
Factor Affecting Corrosion...
Chloride Ion Effect
Chloride may be present in concrete from different sources.
Such as
(a) aggregates containing chlorides salines,
(b) mixing water,
(c) sea-coastal environment,
(d) road de-icing salts, etc.
The chloride ions attack the passive layer and catalyze the
corrosion process. Chloride ions
breakdown the passive layer and cause pitting of the steel
reinforcement.
The following are the major effects of chloride on the
corrosion of reinforcing steel:
(a) Chloride is adsorbed in the protective oxide layer.
(b) The oxidized iron reacts to form soluble intermediate
soluble iron complex at the anode.
Factor Affecting Corrosion...
(c) The complex reacts with moisture to form Fe(OH)2.
The pH is lowered and the concentration of chloride is
increased. Once the chlorides are released on the metal
surface, the process becomes self-generating and no further
chloride .
Effect of Oxygen
Ingress of oxygen to reinforcing steel provide it with a basic
component essential for onset of corrosion.
The void space of concrete contains water, water vapor and
air. Air may diffuse a considerable distance into the mass of
concrete.
The water in contact with air is saturated with oxygen and
the total amount of oxygen would depend on
the total dissolved solids and solubility of oxygen. The
solubility of oxygen is a function of temperature, pressure
and dissolved salt contents.
Factor Affecting Corrosion...
The solubility of oxygen decreases beyond 80°C with a
decrease in the corrosion rate. Areas of concrete with low
water saturation would acquire a higher oxygen concentration.
Differential aeration cells may also be formed on the
reinforcing steel and initiate corrosion .
Cement Types
Chloride ions may react with hydrated tricalcium aluminate
hydrate to form chloroaluminate
(C3A.CaCl2 • 10 H 20) which may contain 75-90% chloride.
The amount of chloride would depend on the total chloride
content, C3A content, and
degree of hydration.
On exceeding the threshold chloride level, the protective
passive layer is destroyed. In general, the chloride ion
concentration decreases with hydration age and increased C3A
concentration.
Factor Affecting Corrosion...
Potential Difference
the difference of potential between two sites at a metal
surface, the greater would be the driving force of corrosion.
Corrosion cell formation due to differences in composition of
metals, aeration, stresses and electrolyte concentration, are
common examples of microcell formation.
In macrocell formation the anodes and cathodes are located in
different steel bars.
Effect of Permeability of Concrete
As the volume of the hydration products is greater than the
volume of concrete grain, the accumulation of hydration
products create a space filling effect. The paste contains two
different forms of pores - capillary pores and gel pores.
(a) Gel pores.-these are fine pores within the particle of
hydrated products filled with water.
(b) Capillary pores-they are generally a thousand times larger
than the gel pores and may be filled with water, water vapor
and air.
Construction Practice
Steel embedded in concrete may be subjected to corrosion if its
surroundings induce corrosion, such as water traps, ingress of
water, oxygen, chloride and water movement.
The construction practice must not allow the freedom of
movement to elements which create an environment for
reinforcement corrosion .
Corrosion Mechanism-Cover to Concrete and Didfusion
The thickness of the cover to concrete affects the time required to
de-passivate steel surface and the rate of reaction.
The concrete cover acts as barrier to the environment. The cover
controls the diffusion of carbon dioxide and chloride to the steel
mainly through the pores in the cement paste to the steel surface.
The diffusion may also occur through the aggregate. The diffusion
path is very slow for very dense and low water cement ratio
concrete.
The thickness of the concrete cover varies with the environment
Method of Corrosion Control of Reinforcing steel
Despite the impressive progress made in controlling the corrosion
of steel in concrete in the last thirty years, reinforcement corrosion
in concrete structures is still a challenging problem.
Cathodic Protection
This is one of the oldest techniques of corrosion protection of steel
in a corrosive environment. It has been widely applied for the
protection of concrete structures.
In principle, a small negative voltage is applied to the steel in
concrete which makes all the steel surface the cathode and
eliminates the anode areas on the steel surface.
Cathodic Protection Technique
The two systems, impressed current and galvanic anode, are used
in protection of steel in soil and
water and also used for the protection of steel embedded in
concrete.
(a) The embedded steel bars are connected to each other in the
Method of Corrosion Control of Reinforcing steel...
Cathodic Protection...
(b) Cathodic protection of steel is considered effective when the
coated steel potential is shifted into the range of 85mVscE to
105mVscE . However, this criterion is not always applicable to
steel in concrete. The uncorroded steel in concrete has a
potential in the from 0 to 0.3 V vs CSE which is about 0.30 to
0.50 more noble than coated steel in soil.
Impressed Current and Sacrificial Anode System
(a) Impressed Current System-An external positive voltage is
applied to an inert anode (silicon, cast iron, titanium) which is
placed in concrete.
Method of Corrosion Control of Reinforcing steel...
Impressed Current and Sacrificial Anode System
(b) Galvanic Anode System- This sacrificial anode system does
not require the use of an external power source as in the
impressed current system.
Method of Corrosion Control of Reinforcing steel...
Criteria for Cathodic protection of Steel in concrete
There are conflicting opinions about the criteria for cathodic
protection during shift in the potential .
A shift in the potential to 850 mVscE may not always be the
best indicator of complete cathodic protection because
hydrogen may enter the steel bar in certain areas because of the
heterogeneous environment of embedded steel bars.
A 300mVscE shift in the negative direction from its original
potential is widely accepted criteria for cathodic protection.
Another criterion is a 100 mV shift of the instant potential on
switching off the current, which in many cases indicates
complete cathodic protection.
experience is the best guide in selecting the criteria for cathodic
protection
Method of Corrosion Control of Reinforcing steel...
Potential Measurements and Potential Mapping
Potential measurement is, in practice, a simple procedure .
The reference electrode (CU-CUSO4) must be in good
electrical contact with the concrete unless the concrete is buried
underground or in the sea (e.g. concrete-covered pipeline).
A high input impedance voltmeter capable of reading 1 mV
resolution is required.
It is necessary to drill a very small hole in the reinforcement to
provide a good electrical contact .
The corrosion status of rebar can be approximated as shown
below:
Method of Corrosion Control of Reinforcing steel...
Corrosion Protection of Rienforcement
Application of Coating
Epoxy coatings offer excellent adhesion and corrosion resistance in harsh
environments. The most commonly used coatings include acrylic,
chlorinated rubber and polyurethane coating.
Inhibitor Treatment
Cathodic, anodic or passivating inhibitors are commonly used to prevent
corrosion of steel reinforcement.
In the anodic inhibitors, calcium nitrite, sodium nitrite, sodium benzoate
and sodium chromate are used. For Cathodic inhibitors amines phosphates,
zincates, aniline and its chloroalkyl nitrosubstituted form and aminoethanol
groups .
because of their direct influence on the passivation of steel surface, anodic
inhibitors provide a larger degree of protection than cathodic inhibtors .
Appropriate dosage of nitrite can control chloride induced corrosion .
Method of Corrosion Control of Reinforcing steel...
Corrosion Protection of Rienforcement
Control of External Factors
The protection of concrete against corrosive agents is as
essential as the mitigation of reinforcement in concrete.
The water-cement ratio, concrete cover thickness, small volume
of pores, degree of saturation of water, temperature and curing
time are important factors to maintain passivation of a steel
surface and minimize the ingress of chloride ions and carbon
dioxide which damage the protective film
The curing process is adversely affected by high temperature
and high winds which create dry conditions. Good curing
improves the permeability of concrete 5-10 fold.
While curing, the effect of admixture, such as fly ash and slags,
must also be considered, as deficient curing makes the concrete
with these
ingredients more permeable to ingress of chloride.
Method of Corrosion Control of Reinforcing steel...
Corrosion Protection of Rienforcement
Use of Sealers and Coatings
The application of coatings and sealers provides resistance to
concrete attack by minimizing the ingress of corrosive species
into concrete and
increasing the durability of the concrete.
The sealers may be applied as lining for the pores
a continuous film of resin on the pore surface after evaporation
from the solvent on the pore surface make the concrete water
repellent .
On evaporation of the solvent from the paint, a continuous film
is formed on the concrete surface.
The film formed on the surface is maintained in an alkaline
environment. Examples are acrylic, epoxy resin, polyester resin
and polyurethane resin.
Method of Corrosion Control of Reinforcing steel...
Corrosion Protection of Rienforcement
Use of Sealers and Coatings
The sealers can also be used to build up reaction product within
the pores which block up the pores.
Silicofluorides are most commonly used. They react with
Ca(OH)2 in the concrete to form silicofluoride compounds
which block up the pores.
Concrete Repair and Rehabilation
It is important to identify the magnitude of the damage, the
effect of damage and the areas requiring repairs.
Two major concrete failures, spalling and cracking, are caused
by reinforcement corrosion, and they require patch repair by a
technique
called patch repair.
The characteristics of damaged areas requiring patch repair
• The reduction in the cover to steel reinforcement thickness. A
thickness of less than10 mm signifies corrosion
• Areas where the half cell potential exceeds 200 mV Q1-CUSO4
(i.e. is more positive than 200 mV)
• Areas where carbonation has ingressed to within 5 mm of the
reinforceme
The depth of carbonation can be determined by testing the
concrete with phenolphthalein, which turns pink in an alkaline
environment and
Concrete Repair and Rehabilation...
Patch Repair
The damaged concrete is removed until the reinforcement bars are
clearly visible. It is removed beyond 50 mm of the corroded
portion.
Rust should be completely removed from the corroded steel by grit-
blasting and coating it after sandblasting with an anticorrosive
primer, if it is to be left overnight in a humid environment.
The repair concrete protects the steel by providing an alkaline
environment which passivates the reinforcing steel.
The aggregate in repairing concrete must be of the same size as the
parent aggregates .
Additional means, such as sealers and coatings, may be
incorporated in the patch repair system.
Material properties, such as elastic modulus, coefficient of thermal
expansion, shrinkage, creep and bonding, must be carefully
considered to make the replacement concrete compatible and allow
Concrete Repair and Rehabilation
Use of Electrochemical Methods
Electrochemical methods, such as cathodic protection and chloride
extraction, can be used as a part of a repair strategy. Cathodic
protection techniques provide alkalinity.
The chloride extraction system removes chloride ions (CI-) from
the concrete electrochemically, and does not allow the breaking of
passive layers.
In yet another process, called re-alkalization, alkaline metal ions
penetrate concrete from an external source of a suitable electrode to
re-alkaline the concrete and regenerate the hydroxyl ions.
Patch Accelerated Corrosion
The patch repair concrete material must be completely chloride-
free and similar in characteristics to the concrete to be replaced,
otherwise the difference of potential between the chloride
contaminated patch and chloride-free patch may induce
accelerated corrosion.
Concrete Repair and Rehabilation...
Patch Accelerated Corrosion...
A potential difference exists between a chloride contaminated
concrete and chloride free patch.
The patch repair concrete material must be completely chloride-
free and similar in characteristics to the concrete to be replaced,
otherwise the difference of potential between the chloride
contaminated patch and chloride-free patch may induce
accelerated corrosion.
A potential difference exists between a chloride contaminated
concrete and chloride free patch. During the process, the positive
Fe2+ ions as a result of anodic reaction combine with the
negative chloride ions from the concrete and form FeCl2 at the
anode .
Upon interaction with water (hydrolysis), the process become self-
generating, and it tarts dissolution. Hydrolysis increases the
dissolution rate and the migration of chloride ions.
Concrete Repair and Rehabilation...
Patch Accelerated Corrosion...
The process becomes self-perpetuating and once initiated, the
process is repeated until the passive layer on concrete is
disrupted.
The repair patch must be completely chloride-free to avoid the
acceleration of corrosion by formation of galvanic cells.
Concrete Repair and Rehabilation...
Principles and Practice of Electrochemical
chloride Removal
In chloride contaminated concrete there is an abundance of
chloride, hydroxyl and calcium ions. Under the influence of an
applied electric field, anions (like Cl-) migrate towards the anode
and the cations to the cathode.
An inert anode and temporary electrolyte are placed temporarily in
the concrete. Catalyzed titanium is used generally as an inert
anode.
Steel has also been used as an anode, but it is consumed after a
period of time. The electrolytes used are generally water, calcium
hydroxide and lithium borate.
The electrolyte can be applied either in tanks clamped to concrete
surface or in absorbent material, like cellulose fibers on the
concrete surface.
Titanium anodes are sandwiched between the layers of felt wetted
Concrete Repair and Rehabilation...
Principles and Practice of Electrochemical chloride
Removal…
In electrochemical chloride extraction, the positive of the power
supply is connected to the anode and negative to the cathode, i.e.
the reinforcing bar.
As soon as the power supply is switched on, chloride ions are
transferred from the contaminated concrete to the anode. The
electrolyte which was temporarily placed would contain the
chloride ion emanating from the contaminated concrete.
A schematic diagram of electrochemical extraction procedure.
CI ions are repelled from the steel bar as follows:
Concrete Repair and Rehabilation...
Principles and Practice of Electrochemical chloride Removal…
If a steel anode is used, a significant amount of current is
consumed by its anodic dissolution, but chlorine gas is not likely
to be generated.
The electrolyte should be maintained at a basic pH to prevent
generation of chlorine. The following are the disadvantages:
(a)the bond strength between rebars and concrete maybe reduced
if high current densities are evolved.
(b) Hydrogen evolution has an adverse effect on pre-stressed steel
and they may be subjected to hydrogen embrittlement because of
the entry of hydrogen into reinforcing bars.
There are, however, more advantages of this technique as
summarized below:
(a)The corrosion rate of reinforcing bar is significantly reduced.
(b) the integrity of the passive film on the steel surface is
maintained.
Concrete Repair and Rehabilation...
Re-Alkalization
Re-alkalization is another form similar to the electrochemical
chloride extraction process, and is used to recreate the alkaline
conditions which are lost due to carbonation.
As stated in an earlier section, the ingress of carbon dioxide
leads to the loss of alkalinity on the reinforcement because of
the fall of pH from 14 to 9 due to the combination of carbon
dioxide with calcium hydroxide [Ca(OH)2] which means loss of
alkalinity from the concrete.
The process of re-alkalization is, therefore, employed to recreate
the alkaline conditions on the reinforcement by attracting Ca ++
ions and Na+ ions (see below) which keeps it in a passive state.
The introduction of alkaline metal ions prevents the occurrence
of re-carbonation.
Concrete Repair and Rehabilation...
Re-Alkalization…
Advantages
Re-alkalization is more economical and simpler than
electrochemical chloride removal process.
In the electrochemical chloride removal process, the evolution
of chlorine gas and its removal prevents ingress of hydrogen
into reinforcement making the process more complex compared
tore-alkalization process.
The re-alkalization technique is gradually gaining popularity in
Europe and the Middle East.
Electrochemical Methods of Evaluation of Rienforcement Corrosion
Polarization Resistance Technique
This is a well established technique applied to determine the
corrosion rate of steel in concrete.
The specimen is polarized to within ±25 mV of the corrosion
potential (ECorr)as the dependence of current with potential in
the vicinity of corrosion potential is linear.
Electrochemical Methods of Evaluation of Rienforcement Corrosion...
Polarization Resistance Technique...
The open circuit potential (ECorr) of the reinforcement is
measured against a reference electrode. Starting from this
potential, the steel reinforcement is polarized to ±25 mV from
£corr at a sweep rate of 5-10 mV/min.
The polarization resistance relates the slope of the polarization
curve in the vicinity of
corrosion potential to the corrosion current.
Electrochemical Methods of Evaluation of Rienforcement Corrosion...
Galvanostatic Plus Technique
The galvanostatic pulse technique is one of the most popular
techniques to estimate the risk of corrosion of reinforcing steel.
A small anodic current pulse for nearly eight seconds is imposed
galvanostatically on to the reinforcement and the resulting
change in potential is measured as a function of time .
Potentials are measured with respect to a CU-C11SO4 electrode.
The applied anodic
current passes through a counter-electrode to the reinforcing
steel in concrete.
The voltage between reinforcing steel and reference electrode is
connected to the AD converter of a computer.
Electrochemical Methods of Evaluation of Rienforcement Corrosion
Impedance Spectroscopy
Impedance spectroscopy has proved a very effective technique
in analyzing corrosion of reinforcement in concrete.
Using Ohm's law one can apply a DC potential to a circuit and
measure the resulting current, from which the resistance can be
calculated. This is illustrated by DC measurements, like
polarization resistance and potentiodynamic polarization .
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