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A

Seminar Report
On
DURABILITY OF REINFORCED CONCRETE STRUCTURE AND
CORROSION MECHANISM
Submitted in partial fulfillment of the requirement of degree of Bachelor of
Technology
In
Civil Engineering

2015-2016

Submitted To:

Submitted By:

Mr. Pradeep Kumar Jain

Raj Rajeshwar Shringi

Lecturer (Department of Civil Engineering)

12EVVCE090

VIT EAST, Jaipur

civil, 4th year, 8th sem

VIVEKANAND INSTITUTE OF TECHNOLOGY, EAST

SISYAWAS, JAGATPURA, JAIPUR 303012

CERTIFICATE

This is to certify that this report entitled by DURABILITY OF REINFORCED


CONCRETE STRUCTURE AND CORROSION MECHANISM which is being submitted
by Raj Rajeshwar Shringi as a part of the course Bachelor of Technology in Civil
Engineering, is a record of bona fide work carried out by him under my guidance and
supervision at Civil Engineering Department, Vivekananda Institute of Technology-East,
Sisyawas, Jagatpura, Jaipur-302035.

Submitted To:

Submitted By:

Mr. Pradeep Kumar Jain

Raj Rajeshwar Shringi

Lecturer (Department of Civil Engineering)

12EVVCE090

VIT EAST, Jaipur

civil, 4th year, 8th sem

Date:
2

Place:

ACKNOWLEDGEMENT
It is great pleasure for me to express my gratitude to Mr. Pradeep Kumar Jain (lecturer)
and all the members of civil department who had cooperated with me in Seminar report. I would
sincerely thank all the teachers & technician for their valuable guidance and cooperation which
helped us to gather the precious knowledge during my report. I thank them from the bottom of
my heart for devoting their precious time for me. My sincere thanks again to Mr. Pradeep
Kumar Jain (lecturer) for providing me wonderful seminar topic and for guiding me to draft
my seminar report.
This work of this magnitude could not have been accomplished without the valuable inputs of
Dr. BHAVNA TRIPATHI for providing all necessary help for this seminar work.

ABSTRACT

For a long time concrete was considered to be very durable material requiring a little or no
maintenance. The assumption is largely true, except when it is subjected to highly aggressive
environment. We forms concrete structures in highly polluted urban and industrial areas,
aggressive marine environments, harmful coastal areas and many other hostile conditions where
other materials of construction are found to be non durable.
The durability of concrete as a construction material and the durability of reinforced concrete
structures under different environmental conditions are probably the least understood attributes of
concrete. No simple theory applies and only incremental advancement based on experiences gained
through practice can be achieved. This paper addresses this issue, with particular emphasis on the
possible improvement of durability through better concrete mix design (or more specifically use of
high-performance concrete), more careful crack control, use of corrosion inhibitors and use of
protective coatings.
Reinforced concrete uses steel to provide the tensile properties that are needed in structural concrete.
It prevents the failure of concrete structures which are subjected to tensile and flexural stresses due to
traffic, winds, dead loads, and thermal cycling. However, when reinforcement corrodes, the
formation of rust leads to a loss of bond between the steel and the concrete and subsequently

delaminating and spalling. If left unchecked, the integrity of the structure can be affected. Reduction
in the cross sectional area of steel reduces its strength capacity.

Key words:

durability, aggressive environment, reinforced concrete, stresses, corrosion

inhibitors.

LIST OF FIGURES

S.NO.

FIGURE NUMBER

DESCRIPTION

PAGE NO.

1.

1.1

CORROSION OF REINFORCEMENT

2.

2.1

CONSEQUENCES OF CORROSION

18

3.1

TYPES OF AGGREGATES

20

4.

3.2

CARBONATION

22

5.

3.3

CRACKS IN CONCRETE

23

6.

3.4

COVER FOR REINFORCEMENT

24

7.

3.5

25

8.

3.6

SPALLING DUE TO FROAST


ACTION
ALKALI AGGREGATE REACTION

31

LIST OF SYMBOLS

S.NO.

SYMBOL

DESCRIPTION

W/C

WATER CEMENT RATIO

20

CH

CALCIUM HYDRATE

29

CSH

CALCIUM SILICATE HYDRATE

29

PAGE NO.

D0

DEPTH OF CARBONATION

30

COEFFICIENT OF CARBONATION

30

TIME OF EXPOSURE

30

INDEX
CONTENT

PAGE NO.

CERTIFICATE

ACKNOWLDGEMENT

ABSTRACT

LIST OF FIGURE

LIST OF SYMBOLS

CHAPTER 1 INTRODUCTION

8-12

1.1 DURABILITY

1.2 DURABILITY IN GENERAL

1.3 CORROSION

1.4 CORROSION MECHANISM

10

CHAPTER 2 LITERATURE REVIEW

13-18

2.1 HISTORY

13

2.2 CONSEQUENCES OF CORROSION

17

CHAPTER 3 RESEARCH AND METHODOLOGY

19-34

3.1 MAIN FACTORS AFFECTING DURABILITY

19

3.2 OTHER FACTORS AFFECTING DURABILITY

19

3.3 TYPES OF DURABILITY

26

3.3.1 PHYSICAL DURABILITY

27

3.3.2 CHEMICAL DURABILITY

27

3.4 CAUSES OF LACK OF DURABILITY

29

CHAPTER 4 METHODS OF CONTROLLING DURABILITY AND CORROSION

34-42

4.1 COMMON METHODS

34

4.2 CORROSION INHIBITORS

36

4.3 CALCIUM NITRATES

40

4.4 CATHODIC PROTECTION

41

CHAPTER 5 CONCLUSION AND REMARKS

43

REFERENCES

44

CHAPTER 1 INTRODUCTION

1.1 DURABILITY
The durability of a cement concrete structure is defined as its ability to resist weathering action,
chemical attack, abrasion, or any other process of deterioration. Durable concrete will retain its
original form, quality and serviceability when exposed to its environment.

1.2 IN GENERAL
The durability of a structure is its ability to serve its intended purposes for a sufficiently long period
of time, or at least during its expected service life. However, although a durable structure is expected
to serve without deterioration to the extent that major repair is required before expiry of its design
life, it must not be presumed that durability is a substitution for good maintenance. Even for a
structure that has been designed and constructed to a high durability standard, regular inspection and
routine maintenance to restore the fitness for purpose of the structure are needed. Hence, when we
come to the durability design of a structure, we must bear in mind the future need for maintenance
and take into account the cost of maintenance in the life cycle cost analysis of the structure.

A reinforced concrete structure may deteriorate because of deterioration of the concrete itself
or because of corrosion of the steel reinforcing bars inside the concrete. Common causes of the
deterioration of concrete include alkali-aggregate reaction, chemical attack, freezing and thawing

action, abrasion and fire. There is often the misunderstanding that carbonation and chloride attack
would cause deterioration of concrete. In actual fact, carbonation and chloride attack would not cause
any harm to the concrete itself; they mainly cause de-passivation of the steel in concrete, which then
leads to steel corrosion. Deterioration of concrete is not a common problem. In most cases, if there is
any problem with the durability of a concrete structure, it is the corrosion of the steel reinforcing bars
that is most likely to be the major cause. This paper focuses on the durability of reinforced concrete
structures in relation to corrosion of steel reinforcement.

1.3 CORROSION OF STEEL


Corrosion is defined as the destruction or deterioration of the material in the environment to which
they are exposed. The steel is not naturally stable and achieve stability by forming iron oxides (FeO,
Fe2O3, Fe3O4 etc) and hence rusting of iron takes place.

FIG. 1.1 CORROSION OF REINFORCEMENT

1.4 CORROSION MECHANISM

The corrosion of steel is an electro-chemical reaction, similar to what is happening in a galvanic cell
(i.e. a battery). When there exists a difference in electrical potential along the steel bar in concrete, an
electro-chemical cell is set up: there form anodic and cathodic regions, connected by the electrolyte
in the form of pore water in the hardened cement paste. The positively charged ferrous ions Fe

++

at

the anode pass into the pore solution while the negatively charged free electron e pass through the
steel into the cathode where they are absorbed by the constituents of the electrolyte and combine with

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water and oxygen to form hydroxyl ions (OH) . These travel through the electrolyte and combine
with the ferrous ions to form ferrous hydroxide, which is converted by further oxidation to rust. The
electro-chemical reactions involved are as follows:

Anodic reactions:
++

Fe Fe + 2 e
++

Fe + 2 (OH) Fe(OH)2 (ferrous hydroxide)


4 Fe(OH)2 + 2 H2O + O2 4 Fe(OH)3 (ferric hydroxide)

Cathodic reaction: 4 e + O2 + 2 H2O 4 (OH)

It can be seen that oxygen is consumed and water is needed for the process to continue. There is no
corrosion in dry concrete probably below a relative humidity of 60% nor is there corrosion in
concrete fully immersed in water, except when water can entrain air, for example by wave action.
The optimum relative humidity for corrosion is 70 to 80%. At higher relative humilities, the diffusion
of oxygen through the concrete is considerably reduced. The differences in electro-chemical potential
can arise from differences in the environment of the concrete, for example when a part of it is
permanently submerged in sea water and a part is exposed to periodic wetting and drying. A similar
situation can arise when there is a substantial difference in the thickness of cover to the steel.
Fortunately, even with a continuous supply of oxygen and water, the steel in concrete does
not necessarily corrode. The concrete cover protects the steel from corrosion not just by hindering the
ingress of deleterious fluids but also by means of passivation. steel embedded in hydrating cement
paste rapidly forms a thin passivating layer of oxide, which strongly adheres to the underlying steel
and gives it complete protection from reaction with oxygen and water, i.e., from corrosion. This state

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of the steel is known as passivation. Maintenance of passivation is conditional on an adequately high


pH (or, in other words, high alkalinity) of the pore water in contact with the passivating layer.
Basically, concrete is alkaline because of the presence of lime, i.e. Ca(OH) 2, which is liberated as a
byproduct during cement hydration. The pH of the pore water in hardened Portland cement paste is
initially around 12.6 to 13.5. This pH is high enough to offer passivation protection to the steel.

However, there is everywhere carbon dioxide, i.e.(CO 2). CO2, in the air. Carbon dioxide
reacts with moisture to form carbonic acid, which then reacts with the lime in the pore water of
concrete to form calcium carbonate, a neutral product. This is called carbonation. As a result, the
alkalinity of the concrete gradually drops and once the pH is reduced to below around 10, the
passivation protection to the steel will be gone and if there is oxygen and water, the steel will start to
corrode.

Apart from carbon dioxide, chloride ions may also destroy the protective passivity layer on
the surface of embedded steel thereby causing de-passivation. Chloride ions activate the surface of
the steel to form an anode, the passivated surface being the cathode. The reactions involved are as
follows:

++

Fe + 2 Cl FeCl2 (ferrous chloride) FeCl2 + 2 H2O Fe(OH)2 + 2


HCl

Thus, the chloride ion Cl is regenerated so that the rust contains no chloride, although ferrous
chloride is formed at the intermediate stage.

Rust has a lower density than steel. Hence, as corrosion takes place, the volume increases and
since the expansion is restrained by the surrounding concrete, bursting stresses are induced, resulting
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in cracking, spalling or delamination of the concrete cover. This makes it easier for aggressive agents
to ingress towards the steel, with a subsequent increase in the rate of corrosion. In other words, once
corrosion starts, it will accelerate.

CHAPTER 2 LITRATURE REVIEW

2.1 HISTORY
Franois Coignet was a French industrialist of the nineteenth century, a pioneer in the
development of structural, prefabricated and reinforced concrete. Coignet was the first to use
iron-reinforced concrete as a technique for constructing building structures. In 1853 Coignet uilt
the first iron reinforced concrete structure, a four story house at 72 rue Charles Michels in the
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suburbs of Paris.Coignet's descriptions of reinforcing concrete suggests that he did not do it for
means of adding strength to the concrete but for keeping walls in monolithic construction from
overturning
. In 1854, English builder William B. Wilkinson reinforced the concrete roof and floors in the
two-storey house he was constructing. His positioning of the reinforcement demonstrated that,
unlike his predecessors, he had knowledge of tensile stresses
Joseph Monier, a French gardener and known to be one of the principal inventors of reinforced
concrete, was granted a patent for reinforced flowerpots by means of mixing a wire mesh to a
mortar shell. In 1877, Monier was granted another patent for a more advanced technique of
reinforcing concrete columns and girders with iron rods placed in a grid pattern. Though Monier
undoubtedly knew reinforcing concrete would improve its inner cohesion, it is less known if he
even knew how much reinforcing actually improved concrete's tensile strength.
Before 1877 the use of concrete construction, though dating back to the Roman Empire and
reintroduced in the mid to late 1800s, was not yet a proven scientific technology.
American New Yorker Thaddeus Hyatt published a report titled An Account of Some
Experiments with Portland-Cement-Concrete Combined with Iron as a Building Material.

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G. A. Wayss was a German civil engineer and a pioneer of the iron and steel concrete
construction. In 1879 Wayss bought the German rights to Monier's patents and in 1884 started
the first commercial use for reinforced concrete in his firm Wayss & Freytag. Up until the 1890s
Wayss and his firm greatly contributed to the advancement of Monier's system of reinforcing and
established it as a well-developed scientific technology.
Ernest L. Ransome was an English-born engineer and early innovator of the reinforced concrete
techniques in the end of the 19th century. With the knowledge of reinforced concrete developed
during the previous 50 years, Ransome innovated nearly all styles and techniques of the previous
known inventors of reinforced concrete. Ransome's key innovation was to twist the reinforcing
steel bar improving bonding with the concrete. Gaining increasing fame from his concrete
constructed buildings Ransome was able to build two of the first reinforced concrete bridges in
North America.One of the first concrete buildings constructed in the United States, was a private
home, designed by William Ward in 1871. The home was designed to be fireproof for his wife.
One of the first skyscrapers made with reinforced concrete was the 16-storey Ingalls Building in
Cincinnati, constructed in 1904
Three physical characteristics give reinforced concrete its special properties:
1.The coefficient of thermal expansion of concrete is similar to that of steel, eliminating large
internal stresses due to differences in thermal expansion or contraction.
2.When the cement paste within the concrete hardens, this conforms to the surface details of the
steel, permitting any stress to be transmitted efficiently between the different materials. Usually
steel bars are roughened or corrugated to further improve the bond or cohesion between the
concrete and steel.
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3.The alkaline chemical environment provided by the alkali reserve (KOH, NaOH) and
the portlandite (calcium hydroxide) contained in the hardened cement paste causes
apassivating film to form on the surface of the steel, making it much more resistant
to corrosion than it would be in neutral or acidic conditions. When the cement paste is exposed to
the air and meteoric water reacts with the atmospheric CO 2, portlandite and the Calcium Silicate
Hydrate (CSH) of the hardened cement paste become progressively carbonated and the high pH
gradually decreases from 13.5 12.5 to 8.5, the pH of water in equilibrium with calcite (calcium
carbonate) and the steel is no longer passivated. As a rule of thumb, only to give an idea on
orders of magnitude, steel is protected at pH above ~11 but starts to corrode below ~10
depending on steel characteristics and local physico-chemical conditions when concrete becomes
carbonated. Carbonatation of concrete along with chloride ingress are amongst the chief reasons
for the failure of reinforcement bars in concrete. The relative cross-sectional area of steel
required for typical reinforced concrete is usually quite small and varies from 1% for most beams
and slabs to 6% for some columns.Reinforcing bars are normally round in cross-section and vary
in diameter. Reinforced concrete structures sometimes have provisions such as ventilated hollow
cores to control teir moisture & humidity.Distribution of concrete (in spite of reinforcement)
strength characteristics along the cross-section of vertical reinforced concrete elements is
inhomogeneous.Mechanism of composite action of reinforcement and concreteA heavy
reinforced concrete column, seen before and after the concrete has been cast in place around the
rebar cage.The reinforcement in a RC structure, such as a steel bar, has to undergo the same
strain or deformation as the surrounding concrete in order to prevent discontinuity, slip or
separation of the two materials under load. Maintaining composite action requires transfer of
load between the concrete and steel. The direct stress is transferred from the concrete to the bar

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interface so as to change the tensile stress in the reinforcing bar along its length, this load transfer
is achieved by means of bond (anchorage) and is idealized as a continuous stress field that
develops in the vicinity of the steel-concrete interface.
Anchorage (bond) in concrete: Codes of specifications
Because the actual bond stress varies along the length of a bar anchored in a zone of tension,
current international codes of specifications use the concept of development length rather than
bond stress. The main requirement for safety against bond failure is to provide a sufficient
extension of the length of the bar beyond the point where the steel is required to develop its yield
stress and this length must be at least equal to its development length. However, if the actual
available length is inadequate for full development, special anchorages must be provided, such as
cogs or hooks or mechanical end plates. The same concept applies to lap splice length mentioned
in the codes where splices (overlapping) provided between two adjacent bars in order to maintain
the required continuity of stress in the splice zone.
Corrosion inhibitors, such as calcium nitrite [Ca(NO2)2], can also be added to the water mix
before pouring concrete. Generally, 12 wt. % of [Ca(NO2)2] with respect to cement weight is
needed to prevent corrosion of the rebars. The nitrite anion is a mild oxidizer that oxidizes the
soluble and mobile ferrous ions (Fe2+) present at the surface of the corroding steel and causes
them to precipitate as an insoluble ferric hydroxide (Fe(OH)3). This causes the passivation of
steel at the anodic oxidation sites. Nitrite is a much more active corrosion inhibitor than nitrate,
which is a less powerful oxidizer of the divalent iron.

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2.2 THE CONSEQUENCES OF CORROSION


The consequences of corrosion are many and varied and the effect of these on the safe reliable
and efficient operation of equipment or structure are often more serious than the simple loss of a
mass of metal. Failure of various kind and the need for expensive replacement 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.

18

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.
Reference to Economy of Metal in Construction and for Security against Fire in the Making of
Roofs, Floors, and Walking Surfaces where he stated his experiments on the behavior of
reinforced concrete.

FIG 2.1 CONSEQUENCESOF CORROSION ON BUILDINGS

19

Chapter 3
RESEARCH AND METHODOLOGY
3.1 Factors affecting durability of structure and responsible for the
deterioration of the structure
Disintegration of concrete and corrosion of reinforcement is the sign of deterioration of concrete
structure. Many researchers have identified, after laboratory investigation and extensive studies
on existing concrete structures, a number of factors affecting the deterioration of reinforced
concrete in such an aggressive environment. The factors may be as follows:
1, improper design of the structure
2, bad detailing of the structure
3, poor material quality
4, bad construction practice
5, accidental loading on the structure
6, aggressive environment

3.2 Other Factor Affecting the Durability of the Reinforced Concrete


1) Aggregate Type
The properties and proportion of constituent materials of concrete have a large influence on the
durability of concrete. As the aggregates occupy up to 80% by volume of concrete, the resistance
surface properties of the aggregates are important parameters affecting durability of concrete. To
ensure adequate durability of marine structure, the aggregates material should be dense, non
shrinking and alkali resistant.

20

FIG 3.1 TYPES OF AGGREGATES


2) Cement Content
The cement content also has a marked influence on the durability of reinforced concrete. Several
researchers and authorities have been given recommendation for the minimum cement content of
concrete exposed to different zone of marine environment.

3) Water-Cement (W/C) Ratio


The water-cement ratio influences both the strength and durability of concrete. According to
Abrams Law, the strength of concrete at a given age and normal temperature decrease with
increasing the water-cement ratio assuming full compaction of concrete have been done.
Permeability of concrete to water depends mainly on the W/C ratio, which determines the size,
volume and continuity of the capillary voids. It is clear that even a small increase of W/C ratio
can increase the concrete permeability to a great extent. Again, permeability is the most
important Characteristics determining the long-term durability of reinforced concrete exposed to
seawater as it controls the diffusion of aggressive salt-ions into the concrete. ACI 318-83 requires
21

that normal weight concrete subjected to freezing and thawing in a moist condition should have
a maximum W/C ratio of:
- 0.45 in case of curbs, gutter, guard rail or their sections and
- 0.50 for other elements.

4) Cement Type
The resistance of concrete against the action of various aggressive agencies depends to a great
extent on the type and proportion of cement. Ordinary Portland and pozzolana and sulfate
resisting cement are the various types mainly used in marine concrete construction. Various
researchers assessed the performance of these cements individually by either exposing the mortar
and concrete specimens in the seawater or in its constituent salt solution, to study their strength
and durability characteristics.

5) Air Entrainment
Harden concrete containing entrained air is more uniform, has less absorption and permeability
and is more resistant to the action of freezing and thawing. Normally, about 4-6% of air by
volume of concrete is entrained which is dispersed throughout, the concrete in the form of
minute, disconnect bubble. It has been reported that the amount of entrained air necessary for
imparting the highest resistance to concrete to frost action in the seawater is in the range of 1020% which is more then twice as large as concrete with 3-6% air entrained when exposed to
plain water in similar environment. However, the amount of air entrained 10-20% reduces the
compressive strength of concrete to about one-half of the strength without air entrainment.

22

6) Carbonation Process
The hydrated concrete has a tendency of combining with carbon dioxide, CO2present in the
atmosphere and forming carbonates, which partly neutralizes the alkaline nature of concrete.
This process is known as carbonation. When carbonation depth exceeds depth of cover to the
reinforcement, the salt ions find a suitable environment leading to greater corrosion.

FIG. 3.2 CARBONATION PROCESS


7) Quality of Mixing Water
Sea water contains a total 3.5% salinity of which
23

- 78% is NaCl ( i.e. 2.7% of total salinity)


- 15% is MgCl2 and MgSO4
According to ACI 318-83 the mixing water should be potable and free from salts. Giving no
specific reference to sea water, it specifies that mortar cubes made with computable mixing water
shall 7 days and 28 days strength equal to at least 90% of strength of similar specimen made with
potable water.
7) Influence of Crack
Reinforced concrete structure, either reinforced develop unavoidable cracks during their service
life. Cracking may stem from various causes; construction cracks as a result of initial and drying
shrinkage, settlement, and heat of hydration; load cracking during normal service as a result of
flexure, stress reversal, torsion, shear etc. However cracks offer a path to the interior of concrete
for the deactivating and corroding agents.

24

FIG. 3.3 CRACKS IN CONCRETE

8) Age of Immersion
The age of immersion also referred to, as period of procuring is the time duration of concrete
commencing immediately after casting up to the formal curing. In a marine environment,
procuring of concrete can be done with either sea water of fresh water. The dissolved salts start
reaching with the concrete affecting its rate of gain in strength when procuring is done with
seawater.

9) Depth of Cover to the Reinforcement


The thickness of the concrete cover to the steel is an important factor regarding rebar corrosion
in an aggressive environment. It affects the time taken for the salts to penetrate to the steel, and
the subsequent rate of arrival of oxygen at the steel surface as in the case of permeability. Lesser
the cover, shorter the time required to deactivate the embedded steel. Also moisture content of
the cover, defines permeability to surrounding salts and gases.

FIG 3.4 COVER FOR THE REINFORCEMENT

25

10) Diffusion of Salts Under Pressure


The harmful salt ions enter to the body of concrete at various depths under hydrostatic pressure
and also to the embedded steel. This result disintegration of concrete which in turn increase its
permeability and provides greater accesses to the chloride ions for coming in contact with steel.
But due to limited availability of oxygen, the corrosion process is often ineffective.

11) Wetting and Drying Cycles


In marine environment, the structural concrete in tidal zone undergoes alternate wetting and
drying process due to tidal action.

12) Freezing and Thawing Cycle


Concrete is greatly affected freeze-thaw cycles. The change in physical state of water ( liquidsolid) inside the mass of concrete results in an increase of volume 9%. The volume change in a
cyclic fashion (freeze-thaw cycle) causes disruption of concrete by dilution process.

FIG 3.5 SPALLING DUE TO FROST ACTION

26

13) Compaction
The concrete as a whole contain voids can be caused by inadequate
compaction. Usually it is being governed by the compaction equipments
used, type of formworks, and density of the steelwork.
14) Chloride Resistance and Steel Corrosion:
Chloride present in plain concrete that does not contain steel is generally not a durability
concern. Concrete protects embedded steel from corrosion through its highly alkaline nature. The
high pH environment in concrete (usually greater than 12.5) causes a passive and noncorroding
protective oxide film to form on steel. However, the presence of chloride ions from deicers or
seawater can destroy or penetrate the film. Once the chloride corrosion threshold is reached, an
electric cell is formed along the steel or between steel bars and the electrochemical process of
carrionsbegins.
15) Curing
It is very important to permit proper strength development aid moisture
retention and to ensure hydration process occur completely.

16) Cover to Reinforcement


Thickness of concrete cover must follow the limits set in codes to prevent the
steel reinforcement from corrosion.

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17) Permeability
It is considered the most important factor for durability. It can be noticed that
higher permeability is usually caused by higher porosity .Therefore, a proper
curing, sufficient cement, proper compaction and suitable concrete cover
could provide a low permeability concrete

3.3 Types of Durability of Concrete


There are many types but the major Concrete Durability types are:
1. Physical durability
2. Chemical durability
3.3.1 Physical Durability
Physical durability is against the following actions
1.

Freezing and thawing action


Since the concrete structure in some rregions exposed to the alternative wetting and drying,
heating and cooling due to the temprture changes which is called freezing and thawing
action.penitration and deposition of salts and other aggressive chemicals, leaching of calcium
hydroxide, action of certain acids, alkali aggregate reaction, abrasion and cavitation etc may
result of freezing and thawing action.
28

2.

Percolation / Permeability of water


The cement paste consist of C-S-H gel , Ca(OH)2 and water filled or empty capillary cavities.
Although gel is porous to the extent of 28% the gel pores are so small that hardly any water can
pass through under normal condition. The permeability of gel pores is estimated to be about
7*10-16 m/s. that is approximately 1/100 of the paste. Formation of microcracks, cracks due to
higher stresses may be the reason for permeability of water.

3.

Temperature stresses i.e. high heat of hydration


On mixing the cement with water rapid heat evolution takes place. C3S is mainly responsible for
the early heat of hydration, C3A for flash setting.
3.3.2 Chemical Durability
Chemical durability is against the following actions

1.

Alkali Aggregate Reaction


some of the aggregates contains reactive silica which when reacts with the alkalies oresent in the
cement i.e, sodium oxide and potassium oxide. Reactive aggregate, high alkali content in cement,
availability of moisture, optimum temperature conditions promotes alkali-aggregate reaction.

2.

Sulphate Attack
Sulfate attack is a chemical breakdown mechanism where sulfate ions attack components of the cement
paste. The compounds responsible for sulfate attack are water-soluble sulfate-containing salts, such as
alkali-earth (calcium, magnesium) and alkali (sodium, potassium) sulfates.
29

3.3.2.1 External attack


This is the more common type and typically occurs where water containing dissolved sulfate
penetrates the concrete. . Sulfate ions that penetrate the concrete react with CH to form
gypsum[1] H+CHCSH2 (Cement chemist notation)
C3A + 3CH2 + 26HC3A.3C.H32
tricalcium aluminate + gypsum ettringite
when concetration of sulfate ions decrease the ettringite breaks down into monosulfates
2C3A + C3A.3C.H32 3C3A.3C.H12
3.3.2.2 Internal attack
This form occurs when the source of sulfates is excess gypsum . The gypsum present in the
concrete it reacts with monosulfates to form ettringite
C3A.3C.H12 + 2CSH2 + 16H C3A.3C.H32
3.

Chloride Ingress
Chloride attack is particularly important aspect of durability as it primarily cause the corrosion of
the reinforcement. Statistics have indicated that over 40% of failure of structures is indirectly due
to chloride attack or corrosion of reinforcement.

4.

Corrosion of reinforcement

30

Corrosion of reinforcement is the electrochemical process. When there is a difference in the


electric potential along the steel reinforcement. The travel of ions through the electrolyte and
combined with the ferrous ion to for ferric hydrauxide which is converted by further oxidation to
Rust.

3.4 Causes for the Lack of Durability in Concrete


1. External Causes:
a.

Extreme Weathering Conditions

b.

Extreme Temperature

c.

Extreme Humidity

d.

Abrasion
2. Internal Causes
a) Physical

Volume change due to difference in thermal properties of aggregates and cement paste

Frost Action

b) Chemical
Alkali Carbonate Reaction

31

Carbonation, i.e. the reaction of the alkalis in concrete with the carbon dioxide in air, does not cause
deterioration of concrete but it has important effects on the durability of reinforced concrete
structures. It gradually reduces the alkalinity of concrete to a pH value of about 9 and once the pH of
the concrete surrounding the steel drops to below 10, the steel will become de-passivated and if water
and oxygen are available the steel will start to corrode.
Carbonation takes place even at small CO 2 concentrations such as are present in rural air,
where the CO2 content is about 0.03%. In an unventilated room, the content may rise to above 0.1%.
In large cities it is on average 0.3% and exceptionally up to 1%. The highest concentration of CO 2 is
probably encountered by the lining of vehicle tunnels. Carbonation occurs progressively from the
outside of concrete exposed to CO 2 but does so at a decreasing rate because CO 2 has to diffuse
through the pore system, including the already carbonated surface zone of concrete. Such diffusion is
a slow process if the pores in hydrated cement paste are filled with water because diffusion of CO 2 in
water is 4 orders of magnitude slower than in air. On the other hand, if there is insufficient water in
the pores, CO2 remains in gaseous form and does not react with the hydrated cement. It follows that
the rate of carbonation depends on the moisture content of the concrete.

The highest rate of carbonation occurs at a relative humidity of around 70% (very close to the yearly
average ambient relative humidity of Hong Kong). Under steady conditions, the depth of carbonation
increases in proportion to the square root of time, as depicted by the following equation:
dc = Ct

in which dc = depth of carbonation, C = carbonation coefficient and t = time of exposure.

Apart from the environmental conditions, the carbonation coefficient is dependent mainly on the
quality, particularly the diffusivity, of concrete. Broadly speaking, in concrete with a W/C ratio of
0.6, a depth of carbonation of 15 mm would be reached after 15 years, but in concrete with a W/C
ratio of 0.45, the same depth of carbonation would not be reached until after 100 years.
32

Since the diffusivity is a function of the pore system of the hardened cement paste, the type of
cement, the W/C ratio and the degree of hydration are the relevant factors influencing carbonation.
As these factors influence also the strength of concrete, it is often said that the rate of carbonation
may be simply taken as a function of the strength grade of concrete. Whilst this postulation applies
quite satisfactorily to laboratory cured concrete, in field cast concrete, which is usually provided with

33

less than ideal curing, the curing conditions also have great effects on the rate of carbonation.

34

Fig 3.6 ALKALI AGGREGATE REACTION

35

With mineral admixtures (also called supplementary cementitious materials), such as pulverized fuel
ash (PFA) and condensed silica fume (CSF), added to the concrete mix, the contents and dosages of
mineral admixtures also have significant effects on the rate of carbonation. Mineral admixtures are
basically pozzolanic materials, which can react with Ca(OH) 2 to produce gel in the cement paste.
Consequently, a concrete containing mineral admixtures will have a lower Ca(OH) 2 content in the
hardened cement paste so that a smaller amount of CO 2 is required to carbonate all the Ca(OH)2 and
the depth of carbonation will tend to increase at a faster rate. On the other hand, however, the
addition of mineral admixtures generally results in a denser microstructure of the hardened cement
paste so that its diffusivity is reduced and the depth of carbonation will tend to increase at a slower
rate. The question is: which of the above two opposing effects is dominant? Conflicting test results
have been obtained by different researchers and according to Neville (Properties of Concrete, 4

th

Edition, 1995), the key factor is the quality of curing. Since the pozzolanic reaction of mineral
admixtures is generally slower than the hydration reaction of cement, concrete mixes incorporating
mineral admixtures generally require longer periods of curing but the required curing was not always
provided in previous tests thereby leading to misleading test results. No general conclusion can be
made. But for concrete with up to 30% PFA added and with actual strength higher than 35 MPa, there
should be no increase, or only a marginal increase, in depth of carbonation compared to that of
concrete containing no PFA, if adequate curing has been provided. However, if the required
prolonged curing has not been provided, the carbonation resistance of concrete containing PFA could
be worst.

Like carbonation, chloride attack does not harm the concrete. Chlorides lead to corrosion of
steel inside concrete and it is the corrosion that causes deterioration of reinforced concrete structures.
There are two possible sources of chlorides: internal from the ingredients of the concrete mix and

36

external from the environment. The use of ingredients containing chlorides for concrete is nowadays
severely restricted and thus it may be assumed that the major source of chlorides is from outside.

Two major types of structures are subjected to chloride attack: highway structures treated
with de-icing salts and marine structures in contact with seawater. De-icing salts are not used and
thus only marine structures need to be considered here. However, land structures at close proximity
to the sea have also been found to be contaminated with chlorides, which probably were raised from
the sea by turbulence and carried by wind in the form of air-borne seawater droplets. Air borne
chlorides can travel substantial distances and up to 2 km has been reported (Neville, 1995). The first
author had himself encountered this air-borne chloride problem at a distance of 30 m from the coast.
Hence, it may be advisable to design all land structures within, say, 100 m from the seashore to a
marine structure standard. Field tests are needed to find out the actual variations of the air-borne
chloride content with the height of the sampling location and with the distance of the structure from
the shore so that a more scientific solution can be worked out.

37

CHAPTER 4
CORROSION INHIBITORS AND CONTROL OF DURABILITY

4.1 COMMON METHODS


There are four common methods used to control corrosion. They include protective coatings and
linings, cathodic protection, materials selection, and corrosion inhibitors. Coatings and linings
are principal tools for defending against corrosion. These substances are often applied in
conjunction with cathodic protection systems to provide the most cost-effective protection for a
structure.
Cathodic Protection (CP) is a technology that uses direct electrical current to counteract. the
normal external corrosion of a structure that contains metal, such as an underground petroleum
storage tank or natural gas pipeline. On new structures, CP can help prevent corrosion from
starting; on existing structures; CP can help stop existing corrosion from getting worse.
Materials selection refers to the selection and use of corrosion-resistant materials such as
stainless steels, plastics, and special alloys to enhance the life span of a structure. Some of the
most common materials used in constructing a variety of facilities, such as steel and steelreinforced concrete, can be severely affected by corrosion. Corrosion inhibitors are substances
that, when added to a particular environment, decrease the rate of attack of that environment on a
material such as metal. They can help extend the life of equipment, prevent system shutdowns
and failures, avoid product contamination, prevent loss of heat transfer, and preserve an attractive
appearance of structures.

38

Material selection entails picking an engineering material either metal alloy or non-metal
that is inherently resistant to the particular corrosive environment and also meets other criteria.
Variables that will affect corrosion are established along with materials that may provide suitable
resistance for those conditions. Obviously other requirements such as cost and mechanical
properties of the potential materials must be considered.
Data needed to thoroughly define the corrosive environment include many of its chemical and
physical characteristics plus application variables such as its velocity (or is it ever stagnant?) and
possible extremes caused by upset conditions. Non-corrosion considerations include mechanical
strength, type of expected loading and possibly the compatibility of the different candidates with
the required fabrication method. After these criteria and other more unique ones are considered
the list of materials that can generally satisfy all requirements usually becomes short. Final
selection is then made but trade-offs from optimal meeting of each criterion often are necessary.
Coatings are the most widely used method for controlling corrosion. The possibilities cover a
wide range and include such things as paints of many types, electroplating, weld overlays and
bonding a thin, corrosion-resistant metal or non-metal onto a stronger substrate metal that is
susceptible to corrosion. In many cases the coating simply acts as a barrier between the corrosive
environment and the substrate material. In some cases such as in galvanized steel the coating
(zinc in this case) provides a barrier but it also acts as a sacrificial anodic material to protect the
steel below by preferentially corroding instead of the steel. This effect is cathodic protection.
The coating selection, surface preparation, application and proper quality control throughout the
process to attain an optimal coating for the given application requires special experience. This is
because like selecting inherently resistant materials by the first method there are many
variables to be considered.
39

When using Organic And Inorganic Paint coatings there are engineering standards that aid the
coating specialist. For those coatings the specific surface preparation required on the substrate is
often critical to final success depending on the type of coating being used.

4.2 CORROSION INHIBITORS


Corrosion inhibitors are chemicals that can slow down or prevent corrosion of reinforcing steel
in concrete. Corrosion inhibitors were first investigated in the 1960s. Some early inhibitors
included sodium nitrite and the sodium and potassium salts of chromate and benzoate. Studies
found that the sodium and potassium salts reduced the strength of the concrete and gave mixed
results on corrosion inhibition. However, other inhibitors have shown promise as methods for
protecting reinforced concrete from corrosion damage (Virmani and Clemena 1998). A common
inhibitor used today, calcium nitrite, was developed to be used in concrete as a noncorrosive set
accelerator (Berke and Rosenberg 1989).
Today, corrosion inhibitors are often used in conjunction with other corrosion protection systems,
such as epoxy coated steel. In places, such as the Florida Keys, that have experienced problems
with epoxy-coated steel, inhibitors are used as an alternate corrosion protection system.
Inhibitors are also used in prestressed concrete applications, where epoxy-coated steel is not
often used. Corrosion inhibitors are added to the grout used to fill post-tension ducts (Virmani
and Clemena 1998).
Corrosion inhibiting admixtures are unique among the methods to protect reinforced concrete
from corrosion damage due to the fact that their protection mechanism becomes an integral part
of the concrete matrix (Berke et al. 1988). A corrosion inhibitor is defined as a substance that
will prevent or minimize corrosion. Most inhibitors act by chemically stabilizing the steel
40

surface, although some also act to reduce the permeability of the concrete. Corrosion inhibitors
are generally used as admixtures in concrete for new construction, but they can also be used
repairs by being admixed into concrete for patches, sprayed or painted onto the surface of the
concrete or applied by saturation treatment (Virmani and Clemena 1998).

41

Corrosion inhibitors are typically divided into three categories: anodic inhibitors, cathodic
inhibitors, and organic inhibitors. Anodic inhibitors, made up of chromates, nitrites, molybdates,
alkali phosphates, silicates, and carbonates, act by minimizing the anodic part of the corrosion
reaction. These inhibitors form an insoluble protective film on anodic surfaces to passivate the
steel. Some anodic inhibitors, such as nitrites, can cause accelerated corrosion and pitting if they
are not used in large enough quantities. Cathodic inhibitors, consisting of zinc, salts of antimony,
magnesium, manganese, and nickel, form an insoluble film on the cathodic surfaces of the steel.
They are usually less effective than anodic inhibitors, but are also safer. Organic inhibitors,
including amines, esters, and sulfonates, block both the anodic and cathodic reaction on the
entire surface of the metal (Virmani and Clemena 1998). Organic corrosion inhibitors have been
used in the oil and gas industries for years, but they were not developed for use in reinforced
concrete until the early 1990s. (Nmai et al. 1992) Organic inhibitors can also act as pore
blockers, reducing the permeability of the concrete.
Corrosion Inhibitors are solid, liquid or gaseous compounds that are added in small quantities to
the given corrosive environment to change its interaction with the metal to be protected.
Corrosion is an electrochemical process that consists of an oxidation reaction on the anodic site
(or sites) of the metal plus one or more reduction reactions on the cathodic site (or sites). These
two types of reactions must always occur at the same rate. An effective inhibitor functions by
chemically changing one or both of the two reactions so as to slow their rates. Thus the rate of
the overall corrosion reaction is reduced to practical levels when a proper inhibitor is applied.
Persons that specify inhibitors must have in-depth knowledge. They need to thoroughly
understand what corrosion reactions occur without the use on an inhibitor in a given application,

42

which inhibitors will have the desired control affect in that application and whether or not a
given inhibitor will have extraneous, undesirable effects in the application. Using and
maintaining the correct concentration of inhibitor is essential. Using too much or too little can
each have negative consequences. Inhibitors are most often used in circulating cooling water
systems or to treat steam boiler feedwater before usage in a boiler.

Corrosion Inhibitors are solid, liquid or gaseous compounds that are added in small quantities to
the given corrosive environment to change its interaction with the metal to be protected.
Corrosion is an electrochemical process that consists of an oxidation reaction on the anodic site
(or sites) of the metal plus one or more reduction reactions on the cathodic site (or sites). These
two types of reactions must always occur at the same rate. An effective inhibitor functions by
chemically changing one or both of the two reactions so as to slow their rates. Thus the rate of
the overall corrosion reaction is reduced to practical levels when a proper inhibitor is applied.
Persons that specify inhibitors must have in-depth knowledge. They need to thoroughly
understand what corrosion reactions occur without the use on an inhibitor in a given application,
which inhibitors will have the desired control affect in that application and whether or not a
given inhibitor will have extraneous, undesirable effects in the application. Using and
maintaining the correct concentration of inhibitor is essential. Using too much or too little can
each have negative consequences. Inhibitors are most often used in circulating cooling water
systems or to treat steam boiler feedwater before usage in a boiler.

43

4.3 CALCIUM NITRITE


Currently, there are only a few commercially available corrosion inhibiting admixtures. The most
common example of an anodic inhibitor is calcium nitrite, which has been commercially
available as Darex Corrosion Inhibitor (DCI and DCI-S) from W. R. Grace since 1978. DCI-S is
simply DCI plus a concrete set retarder (Pyc et al. 1999). Calcium nitrite is now also available
from Master Builders as Rheocrete CNI. Both products are approximately 30% calcium nitrite
and 70% water. To function as an inhibitor, enough calcium nitrite must be added to the concrete
mix to counteract both the effect of chloride ions and the fact that calcium nitrite is water soluble
3
3
and will leach out of the concrete over time. The typical dosage is 10 to 30 l/m (2 to 6 gal/yd )
of concrete, depending on the expected chloride exposure level (Virmani and Clemena 1998).

Table 4.1 Calcium Nitrite Dosage Required for

Chloride Ion Concentration at

Protection Against Chloride-Induced Corrosion

Level of Reinforcement

3
(Bentur et al. 1997) Calcium Nitrite Dosage (l/m )

3
(kg/m )

10

3.6

15

5.9

20

7.7

25

8.9

30

9.5

44

Because calcium nitrite raises the corrosion threshold at the reinforcement rather than blocking
chloride ions from entering concrete, it is important that quality concrete be used to keep the
chloride level at the reinforcement from getting too high. A maximum w/c ratio of 0.45 is
recommended for concrete with calcium nitrite (Kaiser 2000). recommended calcium nitrite
dosages needed to protect reinforcement from corrosion for different chloride ion contents.

4.4 CATHODIC PROTECTION:

Cathodic protection is a corrosion control technology with a long history. It functions due to a
fundamental characteristic of corrosion, i.e., when the electrochemical process of corrosion
occurs there is a flow of DC electric current from the surface being attacked. Cathodic protection
(often known as CP) provides a flow of DC current onto the protected surface to counteract
corrosion current flow. The resulting rate of corrosion is greatly reduced to allow practical, longterm use of the protected metal, e.g., for 10 to 20 years or more, although corrosion is not
stopped. The amount of current necessary to be supplied to the surface to control the rate to
practical levels depends on the area exposed. Thus CP is most often used in conjunction with
some type of coating. This greatly lowers the current needed for protection. No coating is 100%
free of small areas where the substrate is exposed. Using CP with a coating means current is only
needed at these bare spots.
There are two types of CP. One is the sacrificial anode (also called galvanic) type in which a
metal more susceptible to corrosion in the given electrolyte is electrically connected to a less
susceptible metal to be protected. The former metal becomes the anode and is consumed over
45

time while the latter metal becomes the cathode in a galvanic corrosion cell. Thus the zinc on
galvanized steel is the anode while the steel substrate as the cathode is protected. The second
type of CP is impressed current CP. Here an electric power rectifier is used to lower the voltage
of AC line voltage feed to it while changing the AC to DC current. The rectifier is connected to
non-consumable anodes that supply DC current to the metal surface to be protected. Each type of
CP has its separate advantages and disadvantage.

46

CHAPTER 5 CONCLUDING REMARKS

The durability of the concrete is an important aspect for determining the life span of the concrete.
Various factors affect the durability of the concrete and as a result of which corrosion of the
reinforcement bar is the common failure.

Corrosion is the process of oxidizing the material in the presence of water content or moisture
contents as the material forms the oxide taking the oxygen from the moisture and hence the
deterioration takes place.

Sulphate attack, carbonation, sulphonation, permeability of concrete, chloride ingress etc are the
main phenomenon which are responsible for the deterioration of the concrete structure.

So to provide a better life span to a concrete structure it is necessary to find out the durability of the
concrete in that particular region knowing the exposure conditions and providing the different

47

methods for the prevention of corrosion in the steel reinforcement such as cathodic protection, by
coating, or by providing corrosion inhibitors.

REFERENCES

[1] Chandramouli K., Srinivasa Rao P. , Pannirselvam N., Seshadri Sekhar T. And Sravana P.(2010)
Strength Properties Of Glass Fibre Concrete Asian Research Publishing Network VOL.5,NO.4,APRIL

2010
[2] Deshmukh S.H., Bhusari J. P, Zende A. M. (2012) Effect of Glass Fibres on Ordinary Portland

cement Concrete IOSR Journal of Engineering June. 2012, Vol. 2(6) pp: 1308-1312 |
[3] Dr. H. Sudarsana Rao, Dr.Vaishali. G.Ghorpade , Dr. H. M. Somasekharaiah (2012) Durability

Studies On Metakaolin Based Glass Fibre Reinforced High-Performance-Concrete


INTERNATIONAL JOURNAL OF ADVANCED SCIENTIFIC RESEARCH AND TECHNOLOGY

ISSUE 2, VOLUME 2 (APRIL 2012) |


[4] Dr.P.Srinivasa Rao, Chandra Mouli .K, Dr. T. Seshadri Sekhar(2012) Durability Studies On Glass
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[7] N. A. Libre, I. Mehdipour, A. Alinejad, N. Nouri (2008) Rheological Properties Of Glass Fiber

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[8] P. Sangeetha (2011) Study On The Compression And Impact Strength Of GFRC With Combination

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| [9] S. Govindarajan, K l. Muthuramu (2012) Comparative Study on Glass Fibre Cum Natural Fibre

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[10] Surendra P. Shah, James I. Daniel, Darmawan Ludirdja (1987) Toughness of Glass Fibre Reinforced

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[11] Vaishali G Ghorpade(2010) An Experimental Investigation On Glass Fibre Reinforced High
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