CHAPTER ONE

INTRODUCTION
1.1 General
The corrosion of the metals especially steel in concrete has received
increasing attention because of its widespread occurrence in certain types of
structures and the high cost of repairs [1]. There are two consequences of
corrosion of steel; first, the products of corrosion occupy a volume several
times larger than the original steel so that their formation results in cracking,
spalling or delaminating of concrete. This makes it easier for aggressive
agents to ingress toward the steel, with a consequent increase in the rate of
corrosion; second, the progress of corrosion at the anode reduces the crosssectional area of steel, thus reducing its load-carrying capacity [2].
Concrete construction in middle east seaboard countries shows an
alarming degree of deterioration within the short span of 10 to 15 years. The
two most familiar modes of concrete deterioration are concrete spalling due to
reinforcing bar corrosion and expansive cracking due to sulfate attack. The
deterioration is accentuated by the climatic environmental conditions which
are characterized by marginal aggregates, high temperature-humidity regimes,
and severe ground and ambient salinity [3].
When steel is embedded in concrete, a passive film develops and
covers the steel surface. Cement paste is alkaline and enables the formation of
the passive thin film coating on steel that protects the steel from corrosion.
The factors that promote corrosion include oxygen, water and aggressive ions
such as chloride. Thus, the corrosion to be occurred need that the steel
reinforcing bar to be depassivated. Furthermore, the presence of high

Chapter One

Introduction

concentration of salts in concrete i.e. resulted in low resistivity will accelerate

the corrosion process of steel [4-6].
The reinforced concrete is so widely used perhaps due to several
characteristics: a) easy to be molded into different shapes and sizes either on
the site or in a precast concrete plant, b) protection of steel against corrosion,
c) good fire resistance, d) low maintenance, e) high water resistance, f) long
service-life, and g) its ease of manufacture at the construction site.

1.2 Corrosion of Steel in Concrete

Concrete protects the embedded reinforcing steel against corrosion due
to the high alkalinity of the pore water of cement paste. Metals corrode in
acids, whereas they are often protected from corrosion by alkalis [4].
Concrete is of an alkaline nature due to the presence of microscopic
pores with high concentrations of soluble calcium, sodium and potassium
oxides. These oxides form hydroxides in presence of water. The pH of pore
water varies from 12.5 to 13.5, and under such conditions a thin oxide layer is
formed on the rebar surface and prevents the iron from dissolution [7]. As
long as the passive film on the reinforcing steel remains intact, the rate of
corrosion is very low. However, if the oxide layer is broken, oxygen will be
able to react with the steel, resulting in corrosion [8]. Significant corrosion
does not occur for steel in concrete that is either very dry or continuously
saturated because both air and water are necessary for corrosion to be
initiated. Steel will remain corrosion resistant in concrete if the concrete cover
prevents air and water from reaching the embedded reinforcement [9].

1.3 Mechanism of Corrosion of Steel in Concrete

The most common form of reinforcing rebar corrosion in aqueous
medium is of an electrochemical nature. This process requiring the presence
2

Chapter One

Introduction

of electrolytic solution and air [10]. In concrete, an electrochemical cell is

setup; there forms anodic and the cathodic regions connected by the
electrolyte in the form of pore water in the hardened cement paste [3].
The corrosion of steel embedded in the concrete in the presence of
oxygen but with absence of chlorides, takes place in several steps:
First step: at the anode, iron is oxidized to the ferrous state and releases
electrons as in the following equations:
Fe Fe++ + 2e

(Oxidation)

(1.1)

Second step: these electrons migrate to the cathode where they reduce
the dissolved oxygen in the pore water to form hydroxyl ions
H2O + 1/2O2 +2e- 2OH-

(oxygen reduction)

(1.2)

Third step: the hydroxyl ions combine with ferrous ions to form fairly
soluble ferrous hydroxide.
Fe++ + 2OH- Fe(OH)2

(Ferrous hydroxide formation)

(1.3)

Fourth step: in the presence of water and oxygen, the ferrous hydroxide
is further oxidized to form Fe2 O 3.
4Fe(OH) 2 + 2H2O +O2 4Fe(OH) 3 (Ferric hydroxide)

(1.4)

2Fe(OH) 3 Fe2O3.H2O + 2H2O

(1.5)

(Rust)

The unhydrated ferric oxide has a volume of about twice that of the
steel it replaced when fully dense. When it becomes hydrated means that the
volume increase at the steel/concrete interface is (2-10) times, Figure (1.1).
This leads to the cracking and spalling of concrete [4].
Chloride ions present in the cement paste surrounding the
reinforcement react at anodic sites to form hydrochloric acid which destroys
3

Chapter One

Introduction

the passive productive film on the steel. The surface of the steel then becomes
activated locally to form the anode, with the passive surface forming at the
cathode; this ensuring corrosion in the form of localized pitting [11]. In the
presence of chlorides, the schematic reactions are:
-

Fe++ + 2Cl FeCl2

(1.6)

FeCl2 +2H2O Fe(OH) 2 + 2H+

(1.7)

Thus, Cl- is regenerated producing hydrochloric acid which resulted in

progressive pitting corrosion of steel [12]. When corrosion products are
deposited, they induce tensile stresses on the surrounding concrete, which
cause cracking to occur.

1.4 Factors Affect Corrosion of Steel in Concrete

There are several factors may promote the corrosion of steel in concrete
depending on the mode of casting and quality of material used. For example
sand and water used for the mix, the salt content in the sand such as
carbonate, chloride and sulfate are the most aggressive species which can be
explained in the following text:
A) Carbonation:
Carbonation occurs when the concrete reacts with carbon dioxide from
the air or water and reduce the pH to about 8.5. At this low pH, the steel is no
longer passive and corrosion may occur. For high quality concrete, in
situation where the rate of carbonation is extremely slow, carbonation is
normally not a problem unless cracking of the concrete has occurred or the
concrete cover is defective or very thin. Carbonation is not a problem in very
dry concrete or in water-saturated concrete. Maximum carbonation rates are
observed at about 50% water saturation [13, 14].

Chapter One

Introduction

The rate of carbonation depends on the following factors [15]: a) The

level of pore water i.e., relative humidity, b) Grade of concrete, c)
Permeability of concrete, d) Degree of the concrete protection, e) Depth of
cover, and f) Life time.

Fig. (1.1) Relative volume of various oxides formed due to corrosion of

iron [10].
B) Chloride Attack:
Chloride can come from several sources. They can be cast into the
concrete due to [16]: a) Deliberate addition of chloride set accelerators
(calcium chloride was widely used until the mid-1970), b) Use of sea water in
the mix; and c) Contaminated aggregates (usually sea dredged aggregates
which were unwashed or inadequately washed). Or they can diffuse into
concrete as a result of: a) Sea salt spray and direct sea water wetting, b)
5

Chapter One

Introduction

Deicing salt, and c) Use of chemicals as in the structure used for salt storage,
brine tanks, aquaria, etc.
Chloride-Induced Corrosion: chloride act as catalysts to corrosion when
there is sufficient concentration at the rebar surface to break down the passive
layer, Figure (1.2), rendering the iron to dissolve into solution and allow the
corrosion process to proceed quickly [4].
On reaching the iron substrate, the chloride ions oxidize the iron to
form ferric chloride (FeCl3) and that draws its unstable ferrous ion into
solution, were it reacts with the available hydroxyl ions to form Fe(OH)2. This
releases the Cl- back into the solution and consumes the hydroxyl ions, as
seen in the following reactions:
2Fe + 6Cl- 2FeCl3 + 6e-

(1.8)

2H2 + O2 + 4e- 4OH-

(1.9)

FeCl3 + 2OH- Fe (OH) 2 + 3Cl-

(1.10)

The electrons released in the oxidation reaction, as shown in the

equation (1.8), flow through the steel to the cathode. This process results in an
increase in the concentration of the chloride ions and a reduction of the pH at
the points of corrosion initiation, probably accounting for the process of
pitting corrosion. Equation (1.10) showed that three chloride ions are released
as a by- product of steel corrosion indicating that once the chloride ions reach
the metal surface, no further chloride ions are required and depending on the
electrical resistivity either general or local corrosion proceeds [5].
The chloride ions play a dominant role in the initiation of reinforcement
corrosion. For this perspective, ACI 318-11, [19] limits the watersoluble
chloride ion content in reinforced concrete exposed to chloride in service, to

Chapter One

Introduction

0.15% by weight of cement as a maximum chloride ion content for corrosion

protection of reinforcement (chloride- free), see Table 1.1.

Fig. (1.2) The breakdown of the passive layer and recycling chlorides
[4].
C) Sulfate Attack
Soluble sulfates, principally those salts of sodium, calcium, and
magnesium, naturally present in many parts of the world. Soils or waters
containing these sulfates are often all are potentially harmful to concrete. The
attack is usually accompanied by an expansion due to the formation of one or
more solid reaction products having a volume greater than that of the solids
entering into reaction. Solutions containing more than 0.5% of sodium,
potassium, or magnesium sulfates may strongly attack concrete [20].
The rate of attack by sulfate-bearing waters proceeding inward from the
surface is dependent on permeability of concrete and the content of tricalcium aluminates (C3A). Cement containing less than 6 percent content of
C3A exhibits strong resistance, but when it exceeds 12 % the concrete is liable
to suffer from disintegration by sulfates [3].
7

Chapter One

Introduction

Table 1.1 Maximum permissible chloride-ion content (wt %) for

corrosion protection [19].
Maximum water-soluble
chloride

Type of member

ions in concrete* %
Prestressed concrete

0.06

Reinforced concrete exposed to chloride in

0.15

service
Reinforced concrete (dry) protected from

1.00

moisture in the service

Other reinforced concrete construction

0.3

*ASTM C1218: standard test method for water-soluble chloride in mortar and
concrete.

1.5 Corrosion Monitoring Techniques

One of the major problems associated with reinforcement corrosion is
that its initiation and early stages of propagation which cannot be detected
visibly. Yet early detection of corrosion in reinforced 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 of all the concrete cover and much of the reinforcement must be
replaced. The currently electrochemical monitoring techniques are described
below [21, 22] : a) Corrosion potential (Half cell potential), b) Linear
polarization resistance (LPR), c) Polarization technique including Tafel plot
and other techniques such as potentiodynamic or potentiokinetics
8

Chapter One

Introduction

polarization, d) Gravimetric technique (weight loss method), and e)

Electrochemical impedance measurements.

1.6 Prevention Methods

Since the late 1960s, when corrosion of steel in reinforced concrete
structures was first recognized as a problem in non-coastal areas, many
methods have been developed with the intent of preventing corrosion from
occurring. These methods can be divided into four different categories, based
on how they provide protection [23]: (1) alternative reinforcement and slab
design, consisting of epoxy-coated steel, galvanized steel, solid stainless steel,
stainless steel-clad, nickel-clad, titanium, copper-clad, and fiber reinforced
plastic reinforcement, and steel-free slabs; (2) barrier methods, including the
use of low permeability concrete, low water/cement ratio mix designs, the use
of mineral admixtures such as silica fume, fly ash, and blast furnace slag,
overlays, waterproof membranes, sealers, and deep polymer impregnation, (3)
electrochemical methods, including cathodic protection and electrochemical
chloride extraction, and (4) corrosion inhibitors offer protection by raising the
threshold chloride concentration level.

1.7 Water Reducing/Plasticizing Admixtures in Concrete

The use of water reducing/plasticizing admixtures which are surface
active (surfactants) result in dispersion the cement particles within the mix.
When these are incorporated into a mortar mix, the admixture particles are
adsorbed onto the surface of the cement particles, as illustrated
diagrammatically in Figure (1.3). The repulsion of the like charges results in a
powerful deflocculating action and hence a more uniform distribution of the
cement particles throughout the mix. This action also frees some of the water
trapped by the flocculation of the cement particles. Consequently, this type of
admixture can be used to reduce the water content leading to an increase in
9

Chapter One

Introduction

the compressive strength of the mix. The actual water reduction achieved by
the use of this type of admixture depends upon the individual mix
composition; typical water reductions are in the range 7.5 - 12.5% [24].
Water reducing admixtures are based on modified lignosulfonic acid
derivatives, hydroxycarboxylic acids or hydroxylated polymers. In addition to
the single function water reducing/plasticizing admixture, multi function
admixtures such as water reducing/air entrainers, water reducing/retarders and
water reducing/accelerators are available [25].

Entrapped
Water

-a-

-b-

Fig. (1.3) a) Flocculating cement particles trapping the mix water [25], b)
The effect of a water reducing admixture on the dispersion of cement
particles [25].

10

Chapter One

Introduction

1.8 The Aims of Present Project

The present research work aimed to fulfill the following tasks:
1. Study of the effect of the high range water reducing admixture (HRWRA)
on concrete properties such as compressive strength, absorption of water, and
its electrical resistance when exposed to the corrosiveness of chloride solution
in the absence and presence of sulfate ions.
2. Study the effect of (HRWRA) additive on the corrosion resistance of
reinforcement concrete in corrosive environments using a corrosion
monitoring technique by installation of electrochemical measurements system
including: a) the half cell potential measurements and b) the accelerated
corrosion test circuit.
A conformation corrosion test by mass loss method according to ASTM Part
10 for steel reinforcement was adopted.

11