CONCRETE TECHNOLOGY

MKAE1153
Chemical Attack
 Learning Outcome
• At the end of the course students should be able to
understand

-Mechanism of chemical attack

-Factors that influence chemical attack

-Differences in acid, sulphate & AAR attack

-Influencing parameters
 Chemical Attack On Concrete
• Durability of a concrete structure is determined by the rate that
concrete is decomposed as a result of chemical reaction.

• A precondition for chemical reactions to take place is the presence of

water in some form (liquid or gas).

• In general, the reaction between the aggressive substance and the

reactive substance takes place as soon as the substances meet.
However, because of the low rate of transport, these reactions often
may take many years to show their detrimental effect.
• The chemical reactions that may lead
to a decrease in quality are well
established.

a. reaction of acids, aluminium

salts, magnesium salts and soft
water with the hardened cement.

b. reaction of sulphates with

aluminates in concrete

c. reaction of alkalis with reactive

aggregates in concrete.
Acid Attack

• The action of acids on the hardened

concrete is the conversion of the
calcium compounds(calcium hydroxide,
calcium silicate hydrate and calcium
aluminatehydrate) to the calcium salts
of the attacking acid.

–Action of hydrochloric acid leads to the

formation of calcium chloride, which is
very soluble.
–Action of sulphuric acid gives calcium
sulphate, which precipitate as gypsum.
–With organic acids: lactic acid leads to
calcium lactates…..
• As a result, the structure of the
hardened cement is destroyed

• The rate of reaction of different

acids with concrete is determined
not so much by the aggressiveness
of the attacking acid, but more by
the solubility of the resulting
calcium salt.
•Magnesium and ammonium salts react in the same manner
as the equivalent acids, so

–ammonium chloride will react as the free hydrochloric acid

–and ammonium nitrate as the free nitric acid.

•Soft water merely dissolves the calcium compounds, as do the

acids.

–result is, the destruction of the hardened cement.

• Portland cement is not acid resistant and acid attack may remove
part of the set cement. Acids are formed by the dissolution in
water of carbon dioxide or sulphur dioxide from the atmosphere.
Acids can also come from industrial wastes. Good dense concrete
with adequate cover is required and sulphate-resistant cements
should be used if necessary.
Corrosion of floodgate due to acidic water
 Sulphate Attack
• Sulphate attacks only certain components in the cement.

• Sulphate attack is characterized by the chemical reaction of

sulphate ions with the aluminate component and ions of
sulphate, calcium and hydroxyl of hardened Portland cement
or

• cement containing Portland clinker (as the reactive

substances), forming mainly ettringite and to a lesser extent
gypsum.
• Sulphates are present in most cements and some aggregates. Sulphates
may also be present in soils, groundwater and sea water, industrial
wastes and acid rain.

• The products of sulphate attack on concrete occupy a larger space than

the original material and this causes the concrete to disintegrate and
permits corrosion of steel to begin.

• Sulphate-resisting Portland cement should be used where sulphates are

present in the soil, water or atmosphere and encounter the concrete.

• Super-sulphated cement, made from blast furnace slag, can also be used
although it is not widely available. This cement can resist the highest
concentrations of sulphates.
• The reaction between these substances, causes expansion of the
concrete, leading to cracking with an irregular pattern. This gives
easier access to further penetration.

• The main parameters influencing the expansion in practice are:

a. exposure conditions,
i.e. severity of attack (amount of aggressive substance)
b. accessibility,
i.e. permeability of concrete (rate of transport)
c. susceptibility of concrete,
i.e. type of cement (amount of reactive substance)
d. amount of water available
Mechanism
• Concrete may to some extent be protected against
sulphate attack, either by choosing

– a type of cement that is impervious to sulphate attack

or
– by ensuring a sufficient degree of impermeability.
– Generally, cement low in C3A are more resistant to
sulfate attack
Fundamental difference between attack by acids and attack by
sulphates and alkalis.

▪ In the acid attack, there is a complete conversion of the hardened

cement, thus destroying the pore system.

▪ Acids react with all the components in cement

▪ With acid attack, the permeability of the sound concrete is

therefore of minor importance, but not the other types.
 Exposure conditions
• Exposure conditions may be modified by the presence of
constituents other than sulphate

• Example -moderating influence of chloride ions caused by the

preferential formation of chloro-aluminate (Fridellsalt), which
does not lead to detrimental expansion.

• Due to this mechanism sea water, which should be classified as

highly aggressive according to its high sulphate content, is only
moderately aggressive. Therefore, sea water, being of great
importance as an exposure medium.
 Accessibility of concrete

• The degree of impermeability

needed for concrete to be sulphate
resistant may be expressed as
limiting values for depth of water
penetration over a fixed period of
time.

• For practical purposes, this is often

translated into limiting values for
W/C ratio or concrete quality.
 Cement type
• The different types of cement may be classified according to their ability to resist
sulphate attack.

• The ASTM limits aluminates to a maximum of 8% for moderate sulphate resistance

(MSR) and to a maximum of 5% for high sulphate resistance (HSR).

• In Europe, a limit of 3% is generally accepted for (high) sulphate resistance.

• Recent research has unanimously shown the good behaviour of blended cement.
– Several national standards recognize Portland blast-furnace cement with a
minimum of 65% slag as HSR.

• MSR class allows other blended cement containing granulated slag or other
pozzolanic material, either natural or synthetic (fly ash and silica fume).
In cases of combined attack, other factors may influence the choice of
cement.

• An example is the different behaviour of low alumina Portland cement

and Portland blast-furnace cement with a high slag content.

• Both are HSR, but they have a very different permeability for chloride
ions (as in sea water or due to de-icing salt);
–low alumina Portland cement results in the highest permeability
towards chloride ions.
 Alkali-Silica Reaction
• The mechanism of alkali attack resembles that of sulphate
attack because the attack is only on certain substances in the
concrete.

• The difference between sulphate attack and alkali attack is

that the reactive substance in the former case is in the cement,
and in the latter in the aggregates.
• A chemical reaction can take place between alkali in cement and certain
forms of silica in aggregate.

• The reaction produces a gel which absorbs water and expands in

volume, resulting in cracking and disintegration of the concrete.

• BS8110: Part 2, clause 6.2.5.4, states that the reaction only occurs when
the following are present together:
1. Sufficient amount of alkali in pore fluids
2. Sufficient amount of reactive silica present in aggregates
3. Sufficient amount of water

• The absence of any of the above means that ASR will not take place
ASR can be visualized as a two-
process:

1. Alkalis within the concrete react

with siliceous components of
aggregates to form a gel reaction
product

2. Uptake of moisture by the gel by

osmosis causes expansion of the
gel leading to cracking.
• Visible damage starts with (map cracking), followed by complete disintegration.
• General expansion develops in the direction of least resistance.
• Other typical manifestations are pop-outs and weeping of glassy pearls of varying
composition
Cracks through chert aggregate due to aggregate silica
Reaction
The main parameters influencing the expansion in practice are :-

a. the reactivity of the aggregate, -

the presence of amorphous or
partly crystallized silica
b. the amount and grain size of
reactive aggregate
c. alkali and calcium concentrations in
the pore water
d. the type of cement (rate of transport)
e. exposure conditions (external)
f. the amount of water available
 Alkali Content
• As alkali concentration in pore water is a decisive factor, the
alkali content of concrete at any given time is important. The
content of alkalis in cement is expressed as equivalent sodium
oxide (Na2Oeq):

% Na2Oeq = %Na2O + 0.658%K2O

• Free alkali is mainly supplied by the cement.

• Other sources -influx of alkali-containing water into hardened

concrete
 Exposure Conditions
• Exposure conditions certainly play a role and may be
responsible for the great difference in rate of deterioration of
concrete.

• –For concrete design, judgment of aggregates is based on test

results at constant and high humidity. It is known that
intermittent drying and wetting may lead to greater expansion.

• –A practical implication of influence of exposure is the

possibility of retarding or even preventing a progressing
deterioration by waterproofing the concrete.
 MECHANISMS OF CORROSION OF
REINFORCEMENT - Carbonation

Carbonation is a reaction between acidic gases in the atmosphere and the products of
cement hydration

Carbon dioxide diffuse in concrete react with calcium hydroxide and reduce pH value
(pH < 10)
 Carbonation Of Concrete

• CO2 may penetrate and react with the calcium hydroxide.

the chemical reaction may be described as

• The pH will drop below 9 after the concrete has been totally
carbonated.
• If the pH of concrete drops below 9 at the reinforcement,
or if the chloride content exceeds a critical value , the
passive film and the corrosion protection will be lost.

• Reinforcement corrode, if sufficient moisture and oxygen

are available.
 Carbonation of Concrete

Carbonation is the process by which carbon dioxide from the atmosphere slowly
transforms calcium hydroxide into calcium carbonate in concrete. The concrete itself is
not harmed and increases in strength, but the reinforcement can be seriously affected by
corrosion as a result of this process.

Normally the high pH value of the concrete prevents corrosion of the reinforcing bars by
keeping them in a highly alkaline environment due to the release of calcium hydroxide by
the cement during its hydration .

Carbonated concrete has a pH value of 8.3 while the passivation of steel starts at a pH
value of 9.5. The depth of Carbonation in good dense concrete is about 3 mm at an early
stage and may increase to 6-10 mm after 30 40 years. Poor concrete may have a depth of
Carbonation of 50 mm after say 6 to 8 years. The rate of Carbonation depends on time,
cover, concrete density, cement content, water to cement ratio and the presence of
cracks.
WHY???
 The rate determining process is the diffusion of CO2
into concrete, the rate follows a square root time law

Rate of carbonation
(increase of carbonation
depth with time) ; the
ultimate value decreases
with the permeability of
the concrete, the amount
of carbonizable substance
and increasing
environmental humidity
The concrete quality parameter in relation to
carbonation is the permeability

• Diffusion of CO2 is only possible in air filled pores

– For this reason, totally water saturated concrete will

not carbonate
 Repairs and Remedies
Coating and Treatment
• Control moisture ingress (protective
sheltering, tanking and coatings, shedding
run-off water)

• Surface coating (silanes and siloxanes)

• Saturate concrete with lithium bearing

solution
 Repairs and Remedies
Strengthening

• Complete replacement of structural elements, or their

support by auxiliary construction
Biological Processes In Concrete
• Caused by lichen, moss, algae and roots of plants/trees penetrating
the concrete at cracks and weak spots resulting in bursting forces
• Such growth may also retain water on the concrete surface, leading
to a high moisture content of the concrete
• Growth on concrete structures my lead to mechanical deterioration
roots of plants/trees penetrating into the concrete at cracks and weak spots resulting
in bursting forces
• In practice, the most important type of biological attack on
concrete occurs in sewer systems.
• In anaerobic conditions, hydrogen sulphide (which is itself
not very aggressive for concrete) can be formed from sulphate
or from proteins in the sewage.
• It may be oxidized by bacteriological action to form sulphuric
acid, thus resulting in an acid and sulphate attack on the
concrete above the water level.
Sulphide Generation Mechanism in Sewer Networks
 Problems
1. Describe briefly on attack by acid on concrete.

2. What is the difference between attack by acid compared to attack

by sulphate?

3. Describe the mechanism of attack by alkali on reactive aggregate

4. Draw cracks pattern due to corrosion and AAR

5. Of all the three zones of marine structure. Which part is the most
prone to damage , why?

6. Explain on the mechanism of biological attack

What we need to consider in SEAWATER?