CHLORIDE ATTACK AND SULPHATE ATTACK

CHAPTER: - 1
INTRODUCTION [4]

When a concrete structure is prone to chemical actions its durability gets affected. The
chemicals may cause cracking of concrete, volume change and deterioration of structure. The
life of structure reduces and it can lead to failure of structures.

1.1 Types of Chemical Attacks on Concrete Structures

Following are the different chemical actions on concrete structures

o Chloride attack
o Sulphate attack
o Alkali aggregate reaction
o Carbonation

Fig 1: Loss of concrete cover

provided in a load bearing wall

Source: https://www.i4u.com/2017/04/122525/new-technology-sees-through-concrete-
detect-deterioration-building

Fig 2: Loss of concrete cover

provided in a beam
Source: https://theconstructor.org/concrete/chemical-attacks-types-concrete-
structures/7237/

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CHLORIDE ATTACK AND SULPHATE ATTACK

CHAPTER: - 2
CHLORIDE ATTACK
2.1 Corrosion [5]
Any process of deterioration and consequent loss of a solid metallic material, through
an unwanted chemical or electrochemical attack by its environment, starting at its surface, is
called corrosion.

Corrosion means the disintegration of a material into its constituent atoms due to
chemical reactions with its surroundings. In the most common use of the word, this means a
loss of electrons of metals reacting with water and oxygen. Weakening of iron due to oxidation
of the iron atoms is a well-known example of electrochemical corrosion. This is commonly
known as rusting. This type of damage typically produces oxides and/or salt(s) of the original
metal. Corrosion can also refer to other materials than metals, such as ceramics or polymers.
Although in this context, the term degradation is more common.

Most structural alloys corrode merely from exposure to moisture in the air, but the
process can be strongly affected by exposure to certain substances. Corrosion can be
concentrated locally to form a pit or crack, or it can extend across a wide area to produce
general deterioration. While some efforts to reduce corrosion merely redirect the damage into
less visible, less predictable forms, controlled corrosion treatments such as passivation and
chromate-conversion will increase a material's corrosion resistance.

2.2 Passivity [5]

Passivity occurs when an oxide layer forms a continuous film on a metal surface that
prevents further oxidation (corrosion). Metals that are normally subject to corrosion will
sometimes exhibit passivity.

Passivity is caused by the build-up of a layer of metal oxide on the surface of a metal.
In order to provide passivity, this oxide layer must be both stable and tenacious. It is formed
by corrosion when the products of corrosion are insoluble in the particular environment to
which the metal is exposed. The metal oxide acts as a barrier by separating the metal surface
from its environment and prevents corrosion until the reactants diffuse through the oxide film.
This diffusion can take a very long time or may never occur at all.

Metals such as zirconium, chromium, aluminium and stainless-steel form oxide films
when exposed to the atmosphere or to water. In some cases, the film is so thin that it's invisible
to the naked eye. Nevertheless, it is still very effective in giving these metals passivity.

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CHLORIDE ATTACK AND SULPHATE ATTACK

2.3 Corrosion Reaction [4]

Fig 3: Corrosion reaction

Source: https://www.masterbuilder.co.in/repair-rehabilitation-rcc-structures-damaged-
corrosion/

Corrosion is an electrochemical reaction involving the movement of electrons. Let's first

consider a more familiar electrochemical reaction - that which occurs when electricity comes
out of a battery.

In a battery, electrons build up in the negative end, also known as the anode. The positive
end, known as the cathode, is attractive to electrons due to its positive charge. If the two ends
of the battery are connected with a conductive object, such as a metal wire through which
electrons can flow, the electrons will flow from the anode to the cathode as an electric
current. The battery and the wire make up what is known as an electrolytic cell, which is a
device which causes an electric current to flow.

Corrosion in a metal object, such as a pipe, acts in the same manner. A negative area
of metal (the anode) is connected to a positive area (the cathode) by the pipe wall itself. As a
result, electrons can flow from the anode to the cathode.

In addition to the anode, the cathode, and the connecting conductive material, the
electrochemical reaction requires one more element - the electrolyte. The electrolyte is a
conducting solution, which in the case of a pipe is the water within the pipe with its dissolved
salts. (In a battery, the electrolyte is found within the battery - the "battery acid".) The

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CHLORIDE ATTACK AND SULPHATE ATTACK

electrolyte accepts the electrons from the cathode, making the cathode maintain a positive
charge which draws more electrons to it.

So, in summary, any electrochemical reaction requires four elements, all of which must
be in contact - the anode, the cathode, the conductive material, and the electrolyte. In the
battery, the anode and cathode are the two ends of the battery, the conductive material is a wire
or other object touching both ends, and the electrolyte is found inside the battery. In the case
of corrosion of a pipe, the anode, cathode, and conductive material are all found in the pipe
wall while the electrolyte is the water within the pipe. If any of these four elements, which
make up the corrosion cell, are absent or are not touching each other, then corrosion cannot
occur.

2.3.1 Anodic Reaction

Fe Fe2+ + 2e

Fe++ + 2(OH)- Fe(OH)2

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

In the last section, we discussed the electrical side of the electrochemical reaction
occurring during corrosion. In order for the flow of electrons to occur, however, chemical
reactions must also be happening. In this section, we will consider the chemical reactions
which occur in an iron pipe as it corrodes. Other types of pipes will have different, but
homologous, chemical reactions driving their corrosion.
The main force behind corrosion is the tendency of iron to break down into its natural
state. The iron found in pipe is elemental iron (Fe0) which is unstable and tends to oxidize, to
join with oxygen or other elements. In nature, this oxidation produces an iron ore such as
hematite (Fe2O3), magnetite (Fe3O4), iron pyrite (FeS2), or siderite (FeCO3). In corrosion, the
result of this oxidation is rust, Fe(OH)2 or Fe(OH)3.

Oxidation of the elemental iron occurs at the anode. First, the elemental iron breaks
down as shown below. In this reaction, elemental iron leaves the pipe, so pits form in the pipe's
surface at the anode.

Elemental Iron Ferrous Iron ion + Electrons

Fe0 Fe2+ + 2e-

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CHLORIDE ATTACK AND SULPHATE ATTACK

The reaction produces ferrous iron and two electrons. The electrons are then able to
flow through the pipe wall to the cathode. Meanwhile, the ferrous iron reacts with the water
(the electrolyte) in the pipe to produce rust and hydrogen ions.

Ferrous iron + Water Ferrous hydroxide + Hydrogen ions

Fe2+ + 2H2O Fe(OH)2 + 2H+

The rust builds up a coating over the anode's surface. Ferrous hydroxide may then react
with more water to produce another form of rust called ferric hydroxide (Fe(OH)3). These
layers of rust are what creates the tubercles we mentioned earlier.

Tubercles can become problematic because they decrease the carrying capacity of the
pipe and can be dislodged during high water flows, resulting in red water complaints. But in
the corrosion process, the tubercle actually slows the rate of corrosion by cutting the anode off
from the electrolyte. When the tubercle becomes dislodged and the anode comes in contact
with water again, the corrosion rate increases.

2.3.2 Cathodic Reaction

4e + O2 + H2O 4(OH)-

The electrons from the breakdown of elemental iron flow through the pipe wall to the
cathode. There, they leave the metal and enter the water by reacting with hydrogen ions and
forming hydrogen gas:

Hydrogen ions + Electrons Hydrogen gas

2H+ + 2e- H2

Hydrogen gas will coat the cathode and separate it from the water in a process called
polarization. Just as the build-up of a tubercle breaks the connection between the anode and
the electrolyte and slows the corrosion process, polarization breaks the connection between the
cathode and the electrolyte and slows corrosion.

Dissolved oxygen in the water is able to react with the hydrogen gas surrounding the cathode:

Hydrogen gas + Oxygen Water

2H2 + O2 2H2O

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CHLORIDE ATTACK AND SULPHATE ATTACK

This reaction is called depolarization. Depolarization removes the hydrogen gas

surrounding the cathode and speeds up the corrosion process. So, you can see why water
high in dissolved oxygen is more corrosive.

2.4 Chloride Acting as A Catalyst

Fig 4: Chloride promoting corrosion reaction.

Source: https://eduardodseng.wordpress.com/category/degradation-and-surface-
engineering/
The concentration of chlorides in concrete is not uniform due to the heterogeneity of
the concrete. The chlorides enter the concrete from the exposed surface. These differences in
chloride concentrations establish anodes and cathodes on individual steel bars and result in the
formation of micro cells.

The corrosion of steel in concrete in the presence of chlorides, but with no oxygen (at
the anode), takes place in several steps:

At the anode, iron reacts with chloride ions to form an intermediate soluble iron
chloride complex

Fe + 2Cl- (Fe2+ + 2Cl-) + 2e-

When the iron–chloride complex diffuses away from the bar to an area with higher pH
and concentration of oxygen, it reacts with hydroxyl ions to form Fe(OH)2. This complex
reacts with water to form ferrous hydroxide.

(Fe2+ + 2Cl-) + 2H2O + 2e- Fe(OH)2 + 2H+ + 2Cl-

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CHLORIDE ATTACK AND SULPHATE ATTACK

The hydrogen ions then combine with electrons to form hydrogen gas

2H+ + 2e- H2

As in the case of corrosion of steel without chlorides, the ferrous hydroxide, in the
presence of water and oxygen, is further oxidized to form Fe2O3

4Fe(OH)2 + O2 + H2O 4Fe(OH)3 / 2Fe(OH)3 Fe2O3.2H2O

The corrosion products resulting from the corrosion of steel reinforcing bars occupy a
volume five to ten times that of the original steel. This increase in volume induces stresses in
the concrete that result in cracks, delamination and spalls. If left untreated, the process
continues which further accelerates the corrosion process by providing an easy pathway for
water and chlorides to reach the steel until the concrete becomes structurally unsound.

2.5 Corrosion Control [4]

Corrosion control in RC structures can be under taken in following ways:

 Prevention during construction of new structure.

 Rehabilitation of existing structure.
2.5.1 Prevention During Construction of New Structure

• Corrosion can be controlled during construction by enhancing the quality of the

material used and adjusting to the local environment.
The following approaches are commonly used:

– Corrosion inhabiting admixtures

– Coating to reinforcement
– Coating to concrete surface
– By use of fly ash-based cement
– By use of Stainless Steel Rebars

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CHLORIDE ATTACK AND SULPHATE ATTACK

2.5.1.1 Corrosion Inhabiting Admixtures [4]

Fig 5: Effect of admixtures on corrosion

Source: https://waset.org/publications/9996810/durability-of-concrete-with-different-
mineral-admixtures-a-review

• Use of corrosion inhabiting admixtures such as Nitrates, Phosphates, Benzoates can

prevent or delay corrosion. (Typical dosage: 10 – 30 lts/m3 of concrete.)
• A corrosion inhibiting admixture for concrete is disclosed comprising a combination
of organic (amines) and inorganic (nitrites) fractions that provide a synergistic effect
when present at a specific ratio. Such a synergistic effect occurs when the amine:
nitrite ratio (% by weight) is between 1.5 to 2.5 resulting in the admixture providing
excellent corrosion inhibiting capabilities.
• There are four major commercially available corrosion inhibitors:
 DCI (Darex Corrosion Inhibitor) and DCI-S
 Rheocrete 222 and Rheocrete 222+
 Armatec 2000, Ferrogard 901, and MCI 2000
 Catexol 1000 Cl

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CHLORIDE ATTACK AND SULPHATE ATTACK

2.5.1.2 Coating to Reinforcement [4]

• 6: Reinforcement without coating

Fig Fig 7: Reinforcement with coating
Source: https://www.researchgate.net/publication/257121418

• Steel can be made more corrosion resistant by altering its structure through
metallurgical process.
• The protective coatings are based on acrylics Such as Silicones, chlorinated rubber,
epoxy phenolic which retains the breathing property of concrete.
• Coating used in the concrete serve the dual purpose of protection and decoration,
increases cleanability by reducing dust.
Material used for coating

 Zinc
 Epoxy
Zinc coating:

• Dipping the steel bars in molten zinc, this results in a coating of zinc bonded to the
surface of steel.
• Since zinc is more corrosive then Iron, Zinc undergoes sacrificial corrosion to save
Iron from corrosion there by preventing the reduction in strength of Iron Bars.

Epoxy coating:

• The bar in the plant is heated to a controlled temperature and epoxy powder is
deposited evenly on the surface of the bar.

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CHLORIDE ATTACK AND SULPHATE ATTACK

Advantages of epoxy coating

• Viscosity – Low
• Chemical Resistance – Good
• Strength – High
• Thermal Shock Resistance – Good
• Impact Resistance – Good
• Thermal Stability – Good
• Heat Resistance – Good
• Corrosion Resistance – Good
Disadvantages of epoxy coating

• Poor oxidative stability and moisture sensitive.

• Thermal stability limited to 350 to 450oF
• Specialty grades are comparatively expensive
2.5.1.3 Coating to Concrete Surface [4]

• The protective coatings are based on acrylics Such as Silicones, chlorinated rubber,
epoxy phenol which retains the breathing property of concrete.

• Coating used in the concrete serve the dual purpose of protection and decoration,
increases clean ability by reducing dust.

Fig 8: Coating of concrete surface

Source: https://www.structuremag.org/?p=11182

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CHLORIDE ATTACK AND SULPHATE ATTACK

2.5.1.4 Use of Fly Ash Based Cement [4]

• Using a Fly Ash concrete with very low permeability will delay the arrival of
carbonation & chlorides at the level of the steel reinforcement.
• Fly ash is a finely divided silica rich powder that, in itself gives no benefits when
added to a concrete mixture, unless it can react with the calcium hydroxide in the first
few days of hydration. Together they form a calcium silica hydrate (CSH) compound
that over time effectively reduces concrete diffusivity to oxygen, carbon dioxide,
water & chloride ions.
• By reducing ion diffusion, the electrical resistance of the concrete also increases.

Fig 9: Penetration of Chloride with The Age of Concrete

Source: https://www.sciencedirect.com/science/article/pii/S0951833908000543
2.5.1.5 Use of Stainless Steel Rebars [4]

Stainless steel is low carbon steel. Stainless is an alloy of iron with chromium content over
10.5%. Chromium is the alloying element that imparts to stainless steel their corrosion
resistance qualities by combining with oxygen to form a thin, invisible, chromium oxide
protective film on the surface. This means improved corrosion resistance.

In the event that the protective (passive) film is disturbed or even destroyed, in the
presence of oxygen in the environment, reform immediately and continue to give maximum
protection.

The protective film is stable and protective in normal atmosphere or mild aqueous
environments but can be improved by higher chromium and by molybdenum, nickel and other
alloying elements. Nickel is added to enhance corrosion resistance and also to improve

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engineering properties (cold and hot working, bending, welding etc.). Addition to molybdenum
enhances resistance to pitting.

This film protective layer is Uniform, Stable, Tenacious, Continuous, Self-repairing

and transparent.

2.5.2 Rehabilitation of Corroded Structure [4]

Chlorides are the most difficult to deal with by any other methods of repair except the
electro-chemical methods. The chlorides could be introduced in the concrete either through
ingredients of concrete during its making or during its service life from the environment to
which the structure is exposed. These methods have also been used for re alkalization of
concrete in contact with steel reinforcement with some success and have enhanced life of
structures by few years. Though the electro-chemical methods are not very commonly used
methods for buildings, yet these have been tried on limited scale and with success. Whereas
these methods have been very successfully used for underground structures, where sufficient
moisture and grounding medium is available.

2.5.2.1 Cathodic Protection

As the steel reinforcements embedded in concrete undergoes corrosion due to an
electrochemical process taking place within the concrete, micro and /or macro galvanic cells
are formed due to various factors related to both concrete as well as
steel. Thus, corrosion current flows form one region of the steel reinforcement called anode to
another region of the steel reinforcement called cathode. Concrete due to pore-water present in
it, acts as the conducting medium for this corrosion process. Normally the region where there
is relatively high concentration of chloride salts (coupled with a lowering of alkalinity due to
carbonation) acts as anode where corrosion occurs. The region where there is relatively lower
level of chloride contamination (alkalinity is also maintained relatively at a higher level) acts
as cathode of the galvanic cell where oxygen reduction reaction occurs. At the anode, iron goes
into solution as ferrous ions as follows:
Fe Fe2+ + 2 e–
At the cathode, hydroxyl ions are produced as follows:
O2 + 2H2O + 4e 4 OH-

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CHLORIDE ATTACK AND SULPHATE ATTACK

Under micro galvanic process, tiny anodes and cathodes are formed and they also
shift positions leading to general corrosion. Under macro-galvanic process, anodes
and cathodes operate at a macro level.

Principle of cathodic protection

The principle of cathodic protection is nothing but applying a direct current (DC source)
in opposition to corrosion current. While applying cathodic protection, the entire steel
reinforcement network is made as cathode while a more active engineering metal (Zinc,
aluminium or magnesium) system (sacrificial anode) or an inert metal system (impressed
current anode) is made as anode. However, zinc, aluminium or magnesium have been
employed either as sacrificial or impressed current anode. A wire mesh of titanium substrate
insoluble anode in conjunction with a suitable rectifier system has been widely used.

After extensive research and testing it has been established that the only rehabilitation
technique that has proven to stop corrosion in salt contaminated bridge decks regardless of the
chloride content of the concrete is the cathodic protection. Once chloride entered into concrete,
other rehabilitation techniques such as overlays, sealers and water proofing membranes were
found no longer effective.

Advantages of cathodic protection:

The major advantages of cathodic protection system as applied to reinforced
concrete;
(i) Chloride ions move away from the steel reinforcement as they are drawn towards
the externally placed anode.
(ii) Passivation of steel reinforcement gets strengthened due to buildup of alkalinity at
the cathode (production of OH- ions)
2.5.2.2 Electrochemical Chloride Acceleration

The chloride ion attacks the passive layer, even though there is no drop in pH. Chlorides
act as an electron carrier to become a catalyst to corrosion. Chloride ions are not consumed in
the process but help to break down the passive layer of iron oxide on the steel. These allow
the corrosion process to proceed quickly.
“Chloride threshold” for corrosion, is given in terms of the chloride/hydroxyl ion ratio.
When the chloride ion concentration exceeds 0.6 of the hydroxyl ion concentration, then the

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CHLORIDE ATTACK AND SULPHATE ATTACK

protective passive layer over the steel reinforcement breaks down. This approximates to a
concentration of 0.4% chloride by weight of cement. The approximation is because:
(a) Concrete pH varies with the cement powder and the concrete mix. A little pH change
causes an appreciable change in OH- concentration and therefore, the threshold moves
radically.
(b) Chlorides can be bound chemically by aluminates available in hydrated cement paste
and physically by absorption on the pore walls. This removes them (temporarily or
permanently) from the corrosion reaction.
(c) In very dry concrete corrosion may not occur even at very high chloride concentration
as the water, presence of which is essential for ionic movement, is missing.
(d) in saturated concrete corrosion may not occur even at a very high chloride
concentration as the oxygen, an essential ingredient for corrosion activity, is missing.

Fig Fig 11: Electrochemical chloride acceleration

Source: https://constructionduniya.blogspot.com/2012/01/prevention-of-concrete-
structures.html

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CHLORIDE ATTACK AND SULPHATE ATTACK

Process
In the process of chloride removal, an external anode is temporary attached to the
concrete surface and the reactions are driven by a DC power supply. Chloride ions are
negatively charged and the electrochemical process can be used to repel the chloride ion from
the steel surface and move it towards an external anode.

One essential requirement for the success of electrochemical treatment is good

electrical continuity to ensure that current flows from the anode to all areas of steel.
Electrical continuity must be checked and, if necessary, established in all applications of
these techniques. If there is any discontinuity, current will short circuit the concrete pore
structure and the ions will not flow.
Anode types
The most popular anode is the coated titanium mesh used for chloride removal. This
is placed inside a cassette shutter. Where the shape of the member is especially difficult, a
sprayed papier-Mache system can be applied over the anode, soaked with the electrolyte.

Side effects
Passing large amount of electricity through concrete can have effects upon its
chemistry and therefore, its physical condition. There are two known side effects of chloride
removal as follows.
 The first is the acceleration of alkali silica reactivity (ASR)
 Reduction in bond at the steel concrete interface.

2.5.2.3 Realkalisation
Realkalisation is non-Destructive Electrochemical Treatment to restore the alkalinity
of carbonated concrete to prevent further corrosion of reinforcement.
In this process, instead of breaking and mechanically replacing a sound but
carbonated concrete, pH of such concrete is increased to more than 12 initially, which favours
the passivation of steel reinforcement with a final value greater than 10.5, which is
considered sufficient to maintain the passivity of reinforcement.
It is indeed an electrochemical process as is the reinforcement corrosion. The
corrosion reaction consists of an anode and a cathode reaction. The anode reaction causes the
steel reinforcement to be dissolved and occurs at sites where concrete has lost its corrosion

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CHLORIDE ATTACK AND SULPHATE ATTACK

protective nature. Simultaneously, the cathode reaction produces hydroxyl ions at other sites
along the steel reinforcement. While the anode reaction has harmful nature, cathode reaction
improves the corrosion protection of steel.

Process:
Realkalisation is performed by applying an electric field between the reinforcement in
the concrete and an anode system consisting an anode mesh embedded in an electrolytic
reservoir and temporarily placed on the concrete surface. During the treatment, electrolyte,
which is sodium carbonate solution, is transported in to carbonated concrete as symbolized by
the penetrating front. The dominant transport mechanism may vary, but electro-osmosis and
migration of ions are the two main contributors. Simultaneously, electrolysis at reinforcement
surface produces alkaline environment, symbolized by a passive barrier around the
reinforcement.

Advantages:

• Non-destructive repair method

• Removes the cause of corrosion
• Architectural and exposed aggregate finishes can be maintained
• No need of expensive structural support
• Lower cost
• Extended service life
• Fast installation and removal
• No permanent maintenance required
• More environmentally friendly

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CHLORIDE ATTACK AND SULPHATE ATTACK

CHAPTER: - 3

SULPHATE ATTACK

Sulphate attack on concrete is a chemical breakdown mechanism where sulphate ions

attack components of the cement paste. The compounds responsible for sulphate attack on
concrete are water-soluble sulphate-containing salts, such as alkali-earth (calcium, magnesium)
and alkali (sodium, potassium) sulphates that are capable of chemically reacting with
components of concrete.

3.1 Forms of Sulphate Attack on Concrete [1]

Sulphate attack on concrete might show itself in different forms depending on:

 The chemical form of the sulphate

 The atmospheric environment which the concrete is exposed to.

3.2 Sources of Sulphates in Concrete [2]

Following are the sources of sulphates which are responsible for sulphate attack:

1. Internal Sources
This is rarer but, originates from such concrete-making materials as hydraulic cements, fly
ash, aggregate, and admixtures.

 Portland cement might be over-sulphated.

 presence of natural gypsum in the aggregate.
 Admixtures also can contain small amounts of sulphates.

2. External Sources
External sources of sulphate are more common and usually are a result of high-sulphate
soils and ground waters, or can be the result of atmospheric or industrial water pollution.

 Soil may contain excessive amounts of gypsum or other sulphate.

 Ground water be transported to the concrete foundations, retaining walls, and other
underground structures.
 Industrial waste waters.
3.3 Mechanism of Sulphate Attack [2]

When sulphates enter into concrete:

 It combines with the C-S-H, or concrete paste, and begins destroying the paste that
holds the concrete together. As sulphate dries, new compounds are formed, often
called ettringite.

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CHLORIDE ATTACK AND SULPHATE ATTACK

 These new crystals occupy empty space, and as they continue to form, they cause the
paste to crack, further damaging the concrete.

The sulphate ion + hydrated calcium aluminate and/or the calcium hydroxide components of
hardened cement paste + water = ettringite (calcium sulphoaluminate hydrate)
C3A.CS.H18 + 2CH +2S+12H = C3A.3CS.H32
C3A.CH.H18 + 2CH +3S + 11H = C3A.3CS.H32
Different sulfates can affect the concrete differently. Magnesium sulfate is the most
severe because of the presence of magnesium ions. These ions can cause additional corrosive
reactions through the formation of Mg(OH)2 and ettringite.
The sulphate ion + hydrated calcium aluminate and/or the calcium hydroxide components of
hardened cement paste + water = gypsum (calcium sulphate hydrate)
Na2SO4+Ca(OH)2 +2H2O = CaSO4.2H2O +2NaOH
MgSO4 + Ca(OH)2 + 2H2O = CaSO4.2H2O + Mg(OH)2

Fig 12: Spalling of Concrete due to Fig 13: Ettringite Deposit Post
Sulphate Attack Sulphate Attack

Source:
https://www.sciencedirect.com/science/artic
le/pii/S0008884606001049
Source:
https://www.shutterstock.com/image-
photo/damages-cracks-structural-
spalling-concrete-slab-
1126184339?src=7qxDelo7mKFAfm
Dac9x-0A-1-0

Fig 13: Enlarged View of Ettringite Deposit in Sulphate Attacked Hardened Concrete

Source: https://www.understanding-cement.com/sulfate.html

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CHLORIDE ATTACK AND SULPHATE ATTACK

3.4 Factors Affecting Sulphate Attack

1. Type of Cement and its Content

The most important mineralogical phases of cement that affect the intensity of sulphate
attack are: C3A, C3S/C2S ratio and C4AF.

Fig 14: Effect of the C3A content in Portland cement on the rate of deterioration of
concrete exposed to sulphate bearing soils

Source: https://theconstructor.org/concrete/sulphate-attack-on-concrete-prevention/2162/

2. Fly ash addition

The addition of a pozzolanic admixture such as fly ash reduces the C 3A content of
cement.

Fig 15: Sulphate expansion of concrete containing low-calcium fly-ash of different

compositions

Source: https://theconstructor.org/concrete/sulphate-attack-on-concrete-prevention/2162/

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CHLORIDE ATTACK AND SULPHATE ATTACK

3. Types of Sulphate and its Concentration

The sulphate attack tends to increase with an increase in the concentration of the
sulphate solution up to a certain level.

4. Other factors
 The level of the water table and its seasonal variation
 The flow of groundwater and soil porosity
 The form of construction
 The quality of concrete

3.5 Prevention of Sulphate Attack

Following measures help to control sulphate attack:
1. Use of Sulphate Resisting Cement

The most efficient method of resisting the sulphate attack is to use cement with the
low C3A content. It has been found that a C3A content of 7% gives a rough division between
cement of good and poor performance in sulphate waters.
2. Quality Concrete

A well designed, placed and compacted concrete which is dense and impermeable
exhibits a higher resistance to sulphate attack. Similarly, a concrete with low water/cement
ratio also demonstrates a higher resistance to sulphate attack.
3. Use of Air-Entrained Admixture

Use of air-entrainment to the extent of about 6% has beneficial effect on the sulphate
resisting qualities of concrete. The beneficial effect is possibly due to reduction of
segregation, improvement in workability, reduction in bleeding and in general better
impermeability of concrete.
4. Use of Pozzolana

Incorporation of or replacing a part of cement by a pozzolanic material reduces the

sulphate attack. Admixing of Pozzolana converts the leachable calcium hydroxide into non-
leachable cementitious product. This pozzolanic action is responsible for impermeability of
concrete. Secondly the removal of calcium hydroxide reduces the susceptibility of concrete to
attack by magnesium sulphate.
5. High Pressure Steam Curing

High pressure steam curing improves the resistance of concrete to sulphate attack.
This improvement is due to the change of C3AH6 into a less reactive phase and also to the
removal or reduction of calcium hydroxide by the reaction of silica which is invariably mixed
when high pressure steam curing method is adopted.

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6. Use of High Alumina Cement

The cause of great resistance shown by high alumina cement to the action of sulphate
is still not fully understood. However, it is attributed in part to the absence of any free
calcium hydroxide in the set cement, in contrast to Portland cement. High alumina cement
contains approximately 40% alumina, a compound very susceptible to sulphate attack, when
in normal Portland cement. But this percentage of alumina present in high alumina cement
behaves in a different way. The primary cause of resistance is attributed to formation of
protective films which inhibit the penetration or diffusion of sulphate ions into the interior. It
should be remembered that high alumina cement may not show higher resistance to sulphate
attack at higher temperature.
7. Use of Surface Coatings
The commonly used concrete structure protective coatings are divided into two
categories, namely, organic and inorganic. Organic protective coatings benefit coated concrete
structures by protecting them from erosion in a sulphate erosion environment and from sulphate
attacks. However, organic coatings easily ages, and its own service life is considerably shorter
than that of concrete structures in an environment of erosion. Thereby organic coatings fail to
provide effective long-term protection for concrete structures in erosion environment.
Inorganic coatings overcome the aging of organic coatings with good effect in coated concrete
structures. However, inorganic coatings are available in a few types only. The commonly used
inorganic coatings are mainly cement-based infiltration crystalline coatings, which enhance the
durability of concrete structures by strengthening the compactness of the concrete and are
mainly used for waterproofing concrete structures. The anti-sulphate erosion performance of
this coating is poor because its main ingredient is still Portland cement; thus, it cannot provide
effective long-term protection for concrete structures against attacks of sulphate erosion.

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CHLORIDE ATTACK AND SULPHATE ATTACK

References:

[1] F. Ming, Y.-S. Deng, and D.-Q. Li, “Mechanical and Durability Evaluation of
Concrete with Sulfate Solution Corrosion,” Advances in Materials Science and
Engineering, vol. 2016, pp. 1–7, 2016.
[2] N. Cefis and C. Comi, “Chemo-mechanical modelling of the external sulfate attack in
concrete,” Cement and Concrete Research, vol. 93, pp. 57–70, 2017.
[3] W. Piasta, “Analysis of carbonate and sulphate attack on concrete
structures,” Engineering Failure Analysis, vol. 79, pp. 606–614, 2017.
[4] “Issue Information: Structural Concrete 5/2017,” Structural Concrete, vol. 18, no. 5,
pp. 649–650, 2017.
[5] J. Liu, Q. Qiu, X. Chen, F. Xing, N. Han, Y. He, and Y. Ma, “Understanding the
interacted mechanism between carbonation and chloride aerosol attack in ordinary
Portland cement concrete,” Cement and Concrete Research, vol. 95, pp. 217–225,
2017.
[6] Petcherdchoo, “Closed-form solutions for modeling chloride transport in unsaturated
concrete under wet-dry cycles of chloride attack,” Construction and Building
Materials, vol. 176, pp. 638–651, 2018.

Video Reference:
[7] https://www.youtube.com/watch?v=cX2FdjV4eOY

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