The 3rd ACF International Conference-ACF/VCA 2008

D.04

CHLORIDE INDUCED CORROSION AND SULPHATE ATTACK –

A LITERATURE REVIEW ON CONCRETE DURABILITY

Abu Saleh- MSc, Member of Institute of Concrete Technology (UK)

Elkem Materials South East Asia, Singapore

ABSTRACT: Concrete durability is the function of its internal pore structure, porosity and the
permeation properties. Improved pore structure, reduced porosity and enhanced permeation
properties lead to the durability of structures.
Chloride induced corrosion is a form of pitting corrosion. Chlorides diffuse through concrete
matrix to reach the reinforcement bar to breakdown the passive oxide layer of the reinforcement
bar to initiate corrosion.
Sulphate ions permeate through the concrete mass in solution to react with the hydration product
of cement. Sulphate ions of sodium, potassium, magnesium and calcium could attack different
phases of the hydration products. Hence, it is important to improve the permeation properties of
the concrete instead of wholly relying on Sulphate resisting cement with low C3A, which is mainly
focused against sodium sulphate attack, ignoring other forms of sulphate ions which could attack
calcium-silicate-hydrate phase, the main hydration product of hydrated cement matrix and also
calcium hydroxide.
It is a common and worrying trend to use Sulphate resisting cement in chloride laden marine
structures, which is not entirely appropriate. Before adopting any materials for a given
environmental exposure conditions, one should consider the mechanisms of the specific
degradation process such as sulphate or chloride attack and take appropriate preventive
measures. Pozzolanic materials such as silica fume and/or other pozzolanic materials should be
incorporated with the Portland cement to improve the microstructure of concrete to improve the
permeation properties and durability.

KEYWORDS: Durability, chloride, sulphate, corrosion, permeability, absorption, diffusion

INTRODUCTION

Understanding the concept of concrete durability and the right specification of materials for
infrastructure project is utmost important to protect the structure from possible adverse effect of
the exposed environment. This paper has reviewed these issues to highlight the importance of
understanding the durability concept and the right approach to specify the right materials at the
right application.

Characteristics of the hardened paste of cement matrix

The main feature of concrete matrix which affects the nature of concrete is its porosity and the
distribution of the pore structure. Most often, durability is synonymous to the porosity of the

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cement paste although the type of cements and their pozzolanic and hydraulic properties are
equally important to achieve the durability.
One of the common properties of cement matrix which affects the durability of concrete is the
bond between the cement matrix and the aggregate interface. As concrete itself is a multi phase
material, the phase behaviours of materials within the concrete, in its both plastic and harden
state, influence the nature of concrete. Bond strength can be significantly determining factors as
concrete structures are tend to fracture along the interface of cement and aggregate at it reaches
its failure capacity.
Being most reactive materials in concrete, cement becomes vulnerable to the aggressive ions
from the environment. Chemical ions like sulphate ions and acids in the presence of moisture can
detrimentally change the chemical composition of the cement matrix and reduce the durable
nature of concrete structure.
By nature, concrete creates a protective passive oxide layer over the reinforcement bar which
protects the steel bar from corrosion and the alkaline behaviour of cement keeps the environment
of cement matrix always high in terms of the pH value. This harmony, however, can be breached
once the chloride content tipped the threshold value or the presence of carbon-di-oxide with
moisture consumes free lime and reduces the pH value to its acidic level.

Durability of concrete and the adverse effects on durability:

Durability can be defined as the ability of concrete to withstand the damaging effects of the
environment and of its service conditions until it reaches a minimum level of performance. [1]
Durability is the performance of material against a complex nature of environmental effects on
structures. Although, concrete or materials can be designed to be durable but in order to get true
improved performances, a holistic approach encompassing the elements of architectural and
structural design, processes of execution, inspection and maintenance procedures should be taken
into consideration. [2]

Figure 1 shows the interrelationships between the main factors related to the durability. It can be
seen that the principal elements of durability consist of the combined transportation of moisture,
chemical ions and heat, both within the concrete matrix and the microclimate - the surroundings
and the parameters which influences the mechanism of transportation e.g. permeability,
absorption and diffusion.
Presence of moisture in the concrete is the most important factor in terms of deterioration of
durability. As the moisture becomes the medium to carry chemicals, it needs an interconnected
pore distribution inside the concrete matrix in order to move around. So the pore type, size,
distribution and cracks including micro and macro cracks are the contributing factors of moisture
transportation and degradation of concrete.

Permeation and transportation mechanism:

Permeation of water and gasses can be divided into three distinct phenomena:

• Permeability
• Absorption
• Diffusion

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Figure 3 has schematically illustrated the transportation mechanism or permeation properties of

gas and liquids through concrete.

DURABILITY

Structural Design Materials Execution Curing

• Form • Concrete • Workmanship • Moisture
• Detailing • Reinforcement • Heat

Nature and distribution of pores

Transportation mechanisms

Concrete Reinforce
deterioration deterioration

Physical Chemical and Corrosion

biological

PERFORMANCE
Resistance Rigidity Surface
condition

Safety Serviceability Appearance

Figure 1: Relationship between the concept of concrete durability and the performance [2]

Figure 2. Illustration of permeability and porosity (after Bakkar) [3]

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CONCRETE
(porous material)
Transport of Gases, Water
and Dissolved Agents

Binding
Mechanisms

Depending on
Depending on

Environmental conditions
Cracks Pore Structure (microclimate)

Filling of Availability and Temperature

Type of Pore size
pores with concentration of water pressure
pores distribution
water and aggressive agents

Permeability

Transported Agent Transportation

Mechanisms

Diffusion Absorption Permeability

Movement of vapour, gas or Movement of aqueous Movement of liquid or gas
ion under concentration gradient solution under capillary action under pressure gradient

Figure 3: Illustration of the permeation properties of concrete [1]

Permeability

Permeability is the property of concrete which quantitively measure the ease of flow under a
pressure differential through the concrete mass.
Permeability is a function of the pressure gradient, capillary pore size and pore interconnections
in the concrete.
Structures subject to water pressure such as dams, tunnel linings, water retaining structures, port,
harbour, off-shore oil platforms are subjected to permeability.

Environmental
Conditions Pressure gradient

Capillary size and

Permeability Aggregate type
interconnectivity

Water/cement
Hydrate structure ratio

Cement type

Figure 4: Factors influencing permeability of concrete [1]

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Absorption:

Absorption is a process in which water will enter into the concrete through its capillary pores due
to capillary action.
Absorption is directly dependent on the moisture gradient, capillary pore size and pore
interconnectivity of concrete.
Structures subject to cyclic wet and dry are affected by absorption.

Environmental
Conditions Moisture gradient

Capillary size and

Aggregate type
interconnectivity

Water/cement
Absorption Hydrate structure
ratio

Cement type
Pore fluid content

Degree of
saturation

Figure 5: Factors affecting absorption of concrete [1]

Diffusion:

Action of concentration gradient of vapour, gas or ions would lead them to pass through concrete
mass, which is diffusion.
Beside concentration gradients, other factors such as capillary pore size, pore interconnection,
degree of reactivity of concrete substrate are important factors to influence diffusion.
Foundation of structures such as bridges and the atmospheric zone of marine off shore structure

Environmental Ionic concentration

Conditions gradient

Capillary size and Aggregate type

interconnectivity
Water/cement
Diffusion
ratio
Hydrate chemistry
Cement type

Pore fluid chemistry

Curing conditions

Figure 6: Factors affecting diffusion of concrete [1]

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Figure 7: Primary transport mechanism of various exposure zone of a concrete off-shore structure [3]

Factors adversely affecting the durability of concrete:

Concrete is vulnerable to the environmental conditions it is exposed to in terms of chemical,

physical and biological degradation. It is necessary to understand these factors by the concrete
designers and specifiers in order to combat the adverse effect throughout the life cycle of
structure.
A list of different category of the adverse factors affecting durability of concrete has been given
below. Two main factors affecting most of the infrastructures are chloride induced corrosion and
sulphate attack. In the following chapters these two phenomena have been discussed with
importance.
1. Physical process in concrete
a. Cracking
b. Freeze thaw attack
c. Abrasion, erosion and cavitations
d. Heat or fire damage
2. Chemical process in concrete
a. Chemical attack
b. Acid attack
c. Sulphate attack
d. Alkali attack
3. Biological process in concrete
4. Corrosion of reinforcement
a. Corrosion due to chloride ions
b. Corrosion due to carbonation
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Corrosion of reinforcement:

Steel in concrete are protected by a microscopic oxide passive layer of film. This passive layer
can be broken down due to carbonation of concrete or by the action of chloride ions. Corrosion
may also start if the alkalinity in concrete which is normally above 12.5 in pH, reduces due to
leaching out of alkalis due to hydrostatic pressure of water. If the pH of the concrete drops below
9 or if the total chloride content exceeds a critical value called chloride threshold, the passive film
and the corrosion protection will be lost. Corrosion products which is basically an iron oxide is
having a bigger volume than the original volume of affected steel and thus the formation of
corrosion products exert an outward bursting pressure, which results to cracks and deterioration
of durability.

Figure 8: Corrosion of bridge structure

Corrosion due to chloride ions: Chloride ions originated from sea water or other sources may
penetrate through the pore by diffusion or may have direct access through cracks to the interior of
the concrete. Although cement has a natural ability to bind chloride ions, but not all the chloride
ions can be bound. There will always exist a dissolution equilibrium between bound chlorides
and free chloride ions in the pore water. Only the free chloride ions are relevant to the corrosion
of the reinforcement.

Corrosion due to carbonation: Carbon-di-oxide from the environment reacts with the free lime,
calcium hydroxide of concrete to form calcium carbonate. As the high alkalinity of concrete is
caused by the presence of calcium hydroxide, consumption of calcium hydroxide by the process
of carbonation reduces the pH which will drop below 9, once the concrete has totally been
carbonated. As the concrete lost its alkalinity, the passive layer of the reinforcement bar breaks
down and in the presence of water and air, corrosion starts.

Mechanism of Chloride Ingress in Concrete

Chlorides can enter into concrete by both absorption and diffusion processes.

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Absorption: A relatively dry concrete surface will promote chloride to enter into the concrete.
Process of capillary absorption is responsible for chlorides in solution to enter into the concrete
matrix.

Diffusion: Once the concrete becomes saturated due the capillary absorption, the process of
diffusion will then kick in. Due to Fick’s law of diffusion, chloride ion will diffuse through the
concrete mass as there will be a concentration gradient of chloride ions from outer surface to the
inner part of concrete, closer to the reinforcement bars.

Forms of Chlorides

There are following three forms of chloride can be existed in concrete mass:
Free Chlorides
They are the most dangerous forms of chlorides in the concrete as upon entering into concrete
free chloride will diffuse through the pore water to attack the reinforcement bar by breaking
down its passive oxide layer.
Physically Adsorbed Chlorides
Weakly bonded Chloride ions can be existed in the concrete due to the chemical composition of
cement hydrate and type of surface area of hydrate. These forms of physically adsorbed
Chlorides have the potential to move toward the reinforcement bar to start corrosion.
Chemically Adsorbed Chlorides
There are strongly chemically bonded chloride ions with the Calcium Aluminium Hydrate to
form Friedell’s salts. These forms of chlorides are safer as they can not proceed to the
reinforcement to induce corrosion.

Chloride-Induced Corrosion
Chloride threshold level:
Chloride threshold level is a critical chloride content to start off corrosion. It is dependent on the
Cl-/OH ratio, total chloride content, acid-soluble chloride content and water soluble chloride
content.

Figure 9: Process of Pitting Corrosion [1]

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Corrosion process:

Chloride-induced corrosion is a very specific type of ‘pitting’ corrosion. Chloride-induced

corrosion is characterised by galvanic action between relatively large areas of passive steel acting
as cathodes and very small, local anodic pits connected by means of an electrolyte (pore fluid).
For initiation of corrosion, the passive oxide layer must be broken down and chloride ions must
activate the steel surface to form an anode, with the passive surface being the cathode.
The important factor here is that chloride ions are regenerated so that the corrosion products do not
contain chlorides. This regeneration forms hydrochloric acid which will severely attack the steel,
forming localised ‘pits’, continued corrosion and eventual reduction in the cross-sectional area of
steel. Figure 9 illustrate the electro-chemical process of the chloride induced corrosion. [1]

Prevention of Chloride Induced Corrosion:

Chloride-induced corrosion can be minimised by addressing the following requirements:

• Preventing Ingress of Chlorides
• Preventing Ingress of Moisture
• Preventing Ingress of Oxygen
Prevention of Chloride and moisture are more practical means than prevention of oxygen.
Pozzolanic materials especially Microsilica has been proven to be very effective to prevent
corrosion induced by the chloride. The main reason is that Microsilica reduces the porosity of
concrete matrix and makes the concrete dense watertight matrix, preventing moisture and
chloride ion to penetrate and diffuse through the concrete mass.
Microsilica also redefine the pore structure by increasing the tortuosity of the pores which further
prevent any ingress of moisture and other harmful elements from the environment.

Sulphate attack on concrete:

Sulphate attack is the chemical reaction between the sulphate ions from the ground-water and the
different hydrate phase of cement hydrate, but mainly calcium aluminate hydrate to form calcium
sulfo-aluminate hydrate, ettringite, or with calcium hydroxide to form gypsum. Initially these
products may results in a void filling but eventually it expand and crack concrete.
Solid salts, such as sulphates, will not directly attack concrete however, when in solution, they
can react with certain components of the cement paste leading to expansion, cracking and
spalling of concrete.
The most common forms of sulphate are:
Sodium sulphate Na2SO4
Potassium sulphate K2SO4
Magnesium sulphate MgSO4
Calcium sulphate CaSO4

The above sulphates are common in natural groundwater conditions and may exist singly or in
combinations. Sulphates may also be present from unnatural sources such as fertilizers
(ammonium sulphate) or contaminants in soils such as industrial effluent. [1]
The essential agents for sulphate attack are sulphate anions. These are transported to the concrete
through diffusion in various concentrations in water, together with cations, the more common of
which are calcium, magnesium and sodium.

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Sulphate attack can be categorised as two separate forms:

1. The well-known ‘conventional form of sulphate attack’ leading to the formation of
ettringite and gypsum
2. The more recently identified type producing thaumasite
Both conventional form and thaumasite sulphate attack can occur together in buried concrete.
Thaumasite sulphate attack can only be occurred at a temperature below 15°C. Generally
sulphate attack can only be identified when the physical signs of degradation such as expansion,
surface erosion or softening of the cement paste matrix are observed.

Figure 10: Severe sulphate attack in a 30-year-old highway bridge sub-structure exposed to
wet, pyritic clay fill [4]

Conventional form of sulphate attack:

The following factors are essential for the conventional form of sulphate attack to occur where
expansive ettringite together with gypsum formed [4]:
a) Source of sulphates, generally from sulphates or sulphides in the ground
b) The presence of mobile groundwater
c) Calcium hydroxide, calcium aluminate hydrate and calcium silicate hydrate (for
magnesium sulphate) in the cement matrix.

Mechanism of sulphate attack:

Sulphate attack is characterised by the chemical reaction between sulphate ions with the
aluminate component, calcium and hydroxyl of hardened Portland cement. The reaction leads to
the formation of expansive ettringite and to a lesser extent, gypsum. The reaction, providing there
is enough water present, will cause expansion leading to cracking. This in turn will allow further
ingress of sulphates and accelerate the degradation process.
Sulphates will attack some or all of the three main hydrate components of hardened concrete:
Calcium hydroxide, calcium aluminate hydrate, calcium silicate hydrate, depending on the type
of sulphate in solution involved. [1]

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Attack of calcium aluminate hydrate (CaO.Al2O3.H2O) components:

Sulphates will attack the calcium aluminate hydrate component, producing calcium
sulfoaluminate (ettringite), an expansive product and soluble hydroxides: e.g.

2(3CaO.Al2O3.12H2O) + 3(Na2SO4.10H2O) 3CaO.Al2O3.3CaSO4.31H2O + 2Al(OH)3 + 6NaOH + 17H2O

Ettringite soluble hydroxides

In the highly alkaline pore solution (pH>10) provided by the sodium, potassium and calcium
hydroxides liberated during the cement hydration reactions, sulphate ions that have penetrated the
hardened concrete react with calcium aluminate hydrate to form calcium sulfoaluminate hydrate
(ettringite, CaO.Al2O3.3CaSO4.31H2O). The formation of this mineral can be destructively
expansive since it has a solid volume greater than the original constituents and it grows as myriad
acicular (needle-shaped) crystals that can collectively generate high internal stresses in the

Attack of Ca(OH)2 components:

Sulphates will attack the calcium hydroxide component in an ‘acid’ type attack,
producing crystalline calcium sulphates (gypsum) and soluble hydroxide: e.g.

Ca(OH)2 + Na2SO4.10H2O CaSO4.2H2O + 2NaOH + 8H2O

concrete. ... Gypsum soluble hydroxide

This reaction product also has a greater solid volume than the original constituents and in some
cases can contribute to degradation of the concrete.

Attack of calcium silicate hydrate (CaO.SiO2.H2O) components:

Certain sulphates such as magnesium sulphate will also attack the calcium silicate
hydrate as well as the calcium aluminate hydrate and calcium hydroxide,
producing very severe sulphate attack and expansive product and soluble
hydroxides: e.g.

3CaO.2SiO2.aq + MgSO4.7H2O CaSO4.2H2O + Mg(OH)2 + SiO2.aq

Low solubility hydroxide

The low solubility of the hydroxide means that the reaction proceeds until
completion resulting in complete destruction of C-S H

If magnesium ions accompany the sulphates, they may also react with calcium hydroxide,
producing brucite (magnesium hydroxide, Mg(OH)2) which, because of its low solubility

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precipitates out of solution, also leading to increase in solid volume. Magnesium ions may also
attack calcium silicate hydrates, the principal bonding material in set concrete.

The first effect of the conventional form of sulphate attack is to increase the strength and density
of the concrete as the reaction products fill the pore space. When it is filled, further ettringite
formation induces expansive internal stresses in the concrete which, if greater than the tensile
strength of the concrete, will expansively disrupt the affected region. This cracking together with
white crystalline accumulations are the characteristic signs of the conventional form of sulphate
attack. [4]

Sulphate resisting cement and the wrong application:

Concrete designers need thorough understanding of the exposure class and the level of risk before
specifying materials for concrete. It has been widely seen of wrong application of products. The
prime example is of using ‘Sulphate resisting Portland cement’ or SRPC in marine environment.
An SRPC or Type V Cement according to ASTM C 150 suggests to have maximum 5% tri-
calcium-aluminate phase in the cement. This is clearly targeting the basic theory of sodium
sulphate attack on Calcium-Aluminate-Hydrate phase of cement hydration. Using a Type V
cement in Sodium sulphate saturated ground where ground water is mobile makes sense, but not
in a chloride laden marine environment. In a marine environment it is the ‘chloride induced
corrosion’ which is the most important factor. In fact C-A-H ions might be a desirable phase in
marine environment, because of its ability to bind the free chloride into Friedell’s salt.
Civil Engineering Department, Hong Kong in their ‘Port Works Design Manual’ has stated
‘where there is a danger or high risk of chloride ingress causing the reinforcement to corrode, the
tri-calcium-aluminate (C3A) component of the cement is very desirable to reduce the amount of
chloride available to promote corrosion. Sulphate-resisting cements, which are low in C3A
content, may not be appropriate and their inclusion in concrete mixes for marine environment
may need to be reviewed carefully before adopting.’ [5]
Focus by both ASTM C150 and ASTM C1157 have been on sodium sulphate ions, mostly
ignoring or not giving priority to other forms of sulphate such as Magnesium, Potassium and
Calcium sulphate ions. The presence of Magnesium sulphate in the ground water could have
more devastative situation as it would potentially attack the Calcium-Silicate-Hydrate phase, the
main phase of hydrated cement paste. It can be seen that suggestions of using Type V or Type
HS/MS cement according to ASTM C 150 and ASTM C1157 would not solve the problem, if not
compound it to a greater extent, if the specifiers failed to understand the mechanism of sulphate
attacks by different types of sulphate ions.
It might be necessary to use SRPC in sodium sulphate ion laden ground, but not in a ground
where other sulphate ions are predominant. Similarly in a marine environment such as port or
bridge structure, specifying Type V or Type MS/HS cement is not only wrong but uncalled-for.

Improved Microstructure of concrete is the key:

Concrete exposed to chloride laden marine environment needs a concrete which would be able to
prevent or slow down the ingress of chloride ions. It has been discussed in the previous chapters
that chloride ions penetrate into concrete through diffusion and absorption phenomena. In another
word a concrete which has improved microstructure with improved permeation properties will be
able to reduce the chloride ingress. A high performance concrete with reduced w/c ratio and by the
additions of pozzolanic material especially Microsilica or Microsilica blended with Fly ash and/or
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GGBS could change the porosity and pore structure and enhance concrete ability to withstand any
physical and chemical attack on concrete including both chloride and sulphate attack.
It has been seen that sub-micron size and shape of Microsilica physically fills the voids in
between cement grains to produce a perfect particle packing which increases the water-tightness,
density, compressive and flexural strength of concrete. The chemically converted Ca(OH)2 into
more C-S-H products also contributes to that objective. Extreme good bonds between interfaces
of cement paste, aggregates and reinforcement bar provides additional coherence which enhances
the properties of durability.
This has been recognized by the owners, designers and authorities around the globe. The Civil
Engineering Department of Hong Kong suggested to use Microsilica in port construction to reduce
the permeability of concrete at a rate of 5 to 10% by weight of total cementitious content. [5]
Other pozzolanic / hydraulic materials such as Fly ash and GGBS should contribute to the
durability of concrete as well, provided the requirement of the consistent quality are met. Double
or triple blends together with Microsilica have been used successfully in many infrastructure
projects around the world.

CONCLUSION

Concrete durability is the function of its internal pore structure, porosity and the permeation
properties. Improved pore structure, reduced porosity and enhanced permeation properties lead
to the durability of structure.
Chloride induced corrosion is a form of pitting corrosion. Chlorides diffuse through concrete
matrix to reach the reinforcement bar to breakdown the passive oxide layer of the reinforcement
bar to initiate corrosion.
Sulphate ions permeate through the concrete mass in solution to react with the hydration product
of cement. Sodium, potassium, magnesium and calcium sulphate could attack different phases of
the hydration products. Hence, it is important to improve the permeation properties of the
concrete instead of using Sulphate resisting cement with low C3A, which is focused against
sodium sulphate attack.
It is not appropriate to use sulphate resisting cement in chloride laden marine environment.
Pozzolanic materials such as Microsilica and other pozzolanic materials should be incorporated
with the Portland cement to improve the microstructure of concrete to improve the permeation
properties and durability.

REFERENCES

1. Dhir, RK, Newlands, MD, ‘CE50017 Concrete Design for Durability – Lecture notes’,
University of Dundee
2. Comite Euro-International Du Beton, ‘Durable Concrete Structures – Design Guide’,
Thomas Telford Services Ltd, ISBN 0 7277 1620 4, pp. 1
3. Concrete Society Report, Permeability Testing of Site Concrete – A Review of Methods
and experience, Technical Report No. 31 (Concrete Society London, August 1988)
4. BRE, ‘Concrete in Aggressive Ground – Special Digest 1:2005, part A, B, C, D, Draft
copy’
5. Port Works Design Manual, Part 1; General Design Considerations for Marine Works,
Civil Engineering Office, Civil Engineering Department, The Government of the Hong
Kong Special Administrative Region (first published May 2002)

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