CHEMICAL DETERIORATION OF CONCRETE

ABSTRACT

Although reinforced concrete has become the material of choice for general
construction, there is a world wide concern about its durability. Good concrete is
relatively durable under different exposure conditions.It is pointed out that
concrete seldom deteriorates due to a single cause. Usually the physical and
chemical causes are intertwined and superimposed on each other. Concrete is
more vulnerable to chemical agents than any other forms of attack Fortunately
serious chemical attacks are experienced by small portion of concrete used in
practice. The chemical causes of deterioration are briefly reviewed in this paper

Key words Sulphate attack ,Alkali-aggregate reaction ,Corrosion of steel

1 INTRODUCTION

Within a short span of approximately one hundred years reinforced Portland

cement concrete has become the material of choice for the construction of a
large variety of structures. Increasing concern that reinforced concrete may not
be a sufficiently durable material is perceived as one of the potential threat to the
glorious future of the concrete industry (Mehta and Gerwick, 1996).For instance
according to a report of the U.S National Materials Advisory Board in 1987,
approximately 253000 concrete bridge decks, some less than 20 years old were
found in varying states of deterioration. A durable concrete which can withstand
the conditions without deterioration is the need of the day. Concrete being a
heterogeneous material, its behaviour under stresses and performance with time
is highly dependent on individual properties and the environment to which it is
exposed in its life time. Serious deterioration of concrete is mainly due to
chemical attack. The major phenomena of deterioration which could occur during
chemical attack are sulphate attack, alkali-silica expansion and corrosion of
reinforcing steel.

2 SULPHATE ATTACK

Portland cement concrete is vulnerable to attack by aqueous solutions of

sulphate salts that occur in some soils and ground waters. The rate and degree
of attack depend upon the amount of available (soluble) sulphate, the presence
of water, the composition of the cement and certain characteristics of the
concrete such as permeability. As the action progresses there is a gradual loss of
strength in the hardened cement paste component so that the concrete will

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ultimately crumble. Concrete elements that may be exposed to attack by
sulphates in certain soils and ground waters include footings, foundation walls,
retaining walls, piers, piles, culverts, pipes and surface slabs. The severest
attack occurs on elements where one side is exposed to sulphate solutions and
evaporation can take place on the other, for example, retaining walls.

2.1 Occurrence of Available Sulphates

Soluble sulphates are frequently present in very high concentrations in soils and
ground waters. They are believed to be associated with the relatively dry climate
and its action in wicking up the soluble sulphates from lower salt-bearing strata.
Surface deposits of such salts, often mainly sodium sulphate, occur in many
areas, and magnesium sulphate may also be present in high concentrations.
Naturally-occurring calcium sulphate such as gypsum has low solubility and do
not by themselves produces a reaction of significant rate. Over a period of time,
however, they may be converted to the more soluble salts such as sodium and
magnesium sulphates.High concentrations of soluble sulphates may be found at
sites where coal has been stored over some years. Marshy ground also is
sometimes high in such salts. Where sulphide-containing ores are present, for
example, the pyrites occurring in certain shale deposits, oxidation to the sulphate
may occur even through bacteriological action. Sewage and other waste
materials sometimes give off sulphur-containing gases that are readily oxidized
to the sulphate.Sea-water attack on concrete has traditionally been treated as a
problem quite distinct from the type of sulphate attack that occurs in soils and
ground waters. The sulphate concentration in sea water (in soluble, available
form) is extremely high and is of the order of concentration that has proved to be
damaging to concrete in groundwater. The fact that much concrete in sea water
is only partly immersed and therefore subject to high moisture intake is certain to
pose a sulphate threat. The problem has, however, been complicated by frost
action, erosion, corrosion of reinforcing steel, and by physical damage due to ice
and other impact and abrasion factors. Such complicating factors may also occur
at soil surfaces where the threat of sulphate attack derives from soils or ground
waters(E.G. Swenson, 1971).

2.2 Mechanism of the Reaction

It has been demonstrated that sulphate attack on concrete results from a
chemical reaction between the sulphate ion and hydrated calcium aluminate
and/or the calcium hydroxide components of hardened cement paste in the
presence of water. The products resulting from these reactions are calcium
sulphoaluminate hydrate, commonly referred to as ettringite, and calcium
sulphate hydrate, known better as gypsum. These solids have a very much
higher volume than the solid reactants and, as a consequence, stresses are
produced that may result in breakdown of the paste and ultimately in breakdown
of the concrete. Magnesium sulphate is more aggressive than sodium sulphate,
and this has led to speculation that the magnesium ion operates in some
separate reaction that can be destructive. This possible second reaction may
account for cases of deterioration where sulphate-resistant cement (low in

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calcium aluminate) has been used and the quality of concrete has not been in
question (E.G. Swenson, 1971).

2.3 Basic Preventive Measures

The sulphate ion, if present in dangerous amounts (concentration values given
later) and in soluble form, can be denied entry to the concrete by methods
involving waterproof coatings or cut-off drainage. Bituminous coatings have been
used with some success, for example, in special installations such as water pipes
buried underground. Water is not only a necessary reactant in sulphate attack in
concrete but also the vehicle that carries the sulphate ion. Water enters concrete
readily through capillary action. Again, waterproof coatings or drainage constitute
the preventive measures. Design of foundation structures should recognize the
need to reduce or eliminate entry of water into the concrete. The calcium
aluminate hydrate reactant derives from cement. In the manufacture of Portland
cement the normal amount of calcium aluminate present can be reduced to
values that are effective in providing resistance to sulphate attack on concrete.
These cements, called "sulphate-resisting cement" by Canadian Standards
Association (CSA) Specifications and Type V by ASTM, have been
manufactured. These cements may have slightly lower strength gain properties
than normal port-land cements. They are inherently low heat cements also, and
have this benefit where concrete elements are massive. Present CSA
specifications place a maximum limit of 5 per cent on C 3A (the calcium aluminate
component) for sulphate-resisting cement. The calcium ion is present in the form
of calcium hydroxide and is an inescapable product of cement hydration. In
special processes, however, even this reactant can be controlled, for example, in
high-pressure steam curing of concrete or in the use of an active pozzolanic
admixture in concrete. The rate and degree of sulphate attack depend on the
concentration of sulphate present, the type and availability of the sulphate ion,
the accessibility of water, and the type of cement and quality of concrete. The
use of sulphate-resisting cement, low water-cement ratio, minimum cement
content, air-entrainment, waterproof coatings, drainage features, and special
attention to reinforcing cover will safeguard the concrete from sulphate attack.

2.4 Significance of Sulphate Concentrations

1 Negligible attack up to 150 ppm sulphate (SO4) in groundwater’s or up to 0.10
per cent sulphate (SO4) in soil
2 Mild but positive where the corresponding values are 150 to 1000 ppm and
0.10 to 0.20 per cent.
3 Considerable attack at 1000 to 2000 ppm and 0.20 to 0.50 per cent
4 Severe over 2000 ppm and over 0.50 per cent.

Salt concentrations may vary seasonally with amount of rainfall and fluctuations
in water table, the concentration increasing in dry periods. Where structures are
only partially immersed or where only one side of a concrete element is in
contact with sulphated water or soil the continuing capillary action through
evaporation on the air side may build up much higher concentrations of sulphate

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within the concrete than would occur where no such driving force or pumping
action exists. Thus, severe attack may occur even when sulphate contents of test
samples are relatively low. For example, cases classified as "mild but positive" on
the basis of concentrations of sulphates in test samples might, under continuous
wicking action, be potentially much more severe and require correspondingly
greater precautions. On the other hand, concrete elements completely immersed
in highly sulphated soils or waters will not normally be subjected to movement
through the concrete. In such cases the attack will be initially rapid at the surface
but will decrease very significantly so that the degree of severity may be
somewhat less than that predicted by concentration criteria. To some extent this
is also true of partly immersed concretes where the surface exposed is small
compared with the total volume of the element. Where the exposed surface is
subjected to a relatively low-drying environment (very high relative humidity)
attack by sulphates may also be slower than would be predicted by
concentration. Flowing water and groundwater under hydraulic head may
increase severity of attack.

2.5 General Recommended Practice

For a given category of severity, judged on sulphate concentrations and
modifying influences, distinction should be made between non-structural
elements and structural reinforced concrete. The latter should, for obvious
reasons, receive stricter precautionary treatment. Where mild attack is
anticipated normal Portland cement may be used, but water-cement ratio should
not exceed 0.50 and a minimum cement content should be specified, e.g., 550 lb
per cu yd for structural concrete. If a sulphate-resisting cement is used, the
minimum cement content may be lower, e.g., 475 lb per cu yd. Where a
considerable degree of attack is expected sulphate-resisting cement should be
used, with a maximum water-cement ratio of 0.50 and minimum cement content
of the order of 550 lb per cu yd.For severe conditions a sulphate-resisting cement
should be mandatory. Water-cement ratio should not exceed 0.45 and cement
contents should be of the order of 600 to 625 lb per cu yd. Placing and
compaction techniques should ensure the lowest possible porosity or
permeability(E.G. Swenson, 1971). These can include the use of an air-
entraining agent, which is generally a mandatory requirement for all concretes
placed in highly sulphated soils. No admixture, however, will provide specific
resistance to sulphate attack although it may improve workability and thereby
density. Present day bitumens, epoxies, and other organic coatings may show
better performance. In any case, they can provide important protection, for
example, where the water table is expected to fall during and after construction.
They can also protect the concrete until it has matured and become more dense
and less permeable.

3 ALKALI-AGGREGATE REACTION

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Alkali-aggregate reaction is a phenomenon that can lead to serious damage in
concrete elements and structures. During the process, also known as ASR,
expansive compounds (gels) form in the concrete matrix over long periods of
time. The expansion produces fissures and exacerbates weathering and
freeze-thaw cycles, shortening the life cycle. ASR development depends
primarily on aggregate and cement type, water-cement ratio and moisture
condition of concrete while in service. The reaction takes place between
reactive siliceous minerals in certain aggregates and OH- ions in the cement
paste. Alkalis (Na+ and K+) from the cement, mixing water, or environment
increase the concentration of OH- ions in the concrete. The OH- ions attack
susceptible aggregate minerals. The damaged framework forms a gel that
absorbs water from the surrounding concrete. The gel expands, generating
pressures that can crack the concrete. The damage may not be visible to the
naked eye for years after the concrete has been placed.

3.1 Identification

Fig.1-4 Alkali-silica reaction of concrete

Alkali-silica reaction is identified by characteristic three-armed cracks (Fig.1)

appearing on the surface of the concrete. The crack pattern may be altered due
to restraint in one direction (as in a pavement), or due to other stresses from
imposed loads. Sometimes you can see gel oozing from the cracks. A closer look
shows that the cracks start from the aggregate particles. There are other possible
causes of three-armed cracks. To confirm that the cracks are caused by alkali-
silica reaction, have a petrographer examine the concrete. A slightly magnified
view of a polished surface will show reaction rims (Fig.2) around the reactive
aggregate particles. In a thin section (Fig.3 and 4), signs of ASR include cracks
originating from the reactive aggregate particles, discolored areas around the
aggregate particles where ASR gel has stained the surrounding paste, and gel
filling the cracks. The petrographer will also be able to identify the type(s) of
reactive mineral(s) causing the problem (Rachel Detwiler, 2003).

3.2 Detection
The first step is to determine whether the aggregates to be used on a project are
susceptible to ASR. Construction Technology Laboratories can provide any or all
of the tests required, as well as recommendations for how best to control any
harmful expansions. The Portland Cement Association recommends analyzing

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the aggregate according to ASTM C 295, "Standard Guide for Petrographic
Examination of Aggregates for Concrete." If the aggregate contains more than
the following quantities of any of these reactive minerals, it is considered
potentially reactive:
1 Optically strained, micro fractured, or microcrystalline quartz exceeding 5.0%
2 Chert or chalcedony exceeding 3.0%
3 Tridymite or crystobalite exceeding 1.0%
4 Opal exceeding 0.5%
5 Natural volcanic glass in volcanic rocks exceeding 3.0%

It is helpful to give this list to the petrographer so s/he knows how much of each
constituent is considered problematic. In addition, the aggregate should also be
tested according to ASTM C 1260, "Standard Test Method for Potential Alkali
Reactivity of Aggregates (Mortar-Bar Method)." Any aggregate having a 14-day
expansion greater than 0.10% is considered potentially reactive. If the aggregate
is determined to be potentially reactive by either of these tests, it may be further
evaluated by ASTM C 1293, "Standard Test Method for Determination of Length
Change of Concrete Due to Alkali-Silica Reaction." An aggregate having a 1-year
expansion greater than 0.04% is considered potentially reactive (Rachel Detwiler,
2003).

3.3 Minimization of the Effects of ASR

If the aggregate is shown to be potentially reactive by these tests, some
mitigation measure must be used to control the expansion and cracking. Low-
alkali cements are sometimes recommended for this purpose, but they are not
always the best or even an adequate solution. Some aggregates are too reactive
to be controlled by low-alkali cement. Also, alkalis can come from other sources
besides the cement. It is better to use supplementary cementitious materials in
some form to control the expansions:
1. Blended cements containing Class F fly ash, natural pozzolans, calcined clay,
silica fume, or slag may be used either alone or in combination with additional
supplementary cementitious materials of the same or different type.
2. Portland cement may be used with one or more supplementary cementitious
materials. Lithium admixtures may also be used.

4 CORROSION OF STEEL IN CONCRETE

The strongly alkaline nature of Ca(OH)2 (pH of about 13) prevents the corrosion
of the steel reinforcement by the formation of a thin protective film of iron oxide
on the metal surface. If the concrete is permeable to the extent that carbonation
reaches the concrete in contact with the steel or soluble chlorides can penetrate
right up to the reinforcement, and water and oxygen are present, then corrosion
of reinforcement will take place. The passive iron oxide layer is destroyed when
pH falls below about 11 and carbonation lowers the pH about 9 (Neville and
Brooks, 1999). The damage to concrete resulting from corrosion of embedded

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steel manifests in the form of expansion, cracking and eventually spalling of the
cover

4.1 Mechanisms Involved in Concrete Deterioration by Corrosion of

Embedded Steel
Corrosion of steel occurs because of electro-chemical action which is usually
encountered when two dissimilar metals are in electrical contact in the presence
of moisture and oxygen. The same process takes place in steel alone because of
differences in the electro-chemical potential on the surface which forms anodic
and cathodic regions, connected by electrolyte in the form of salt solution in the
hydrated cement. The deleterious action of chlorides will aggravate the corrosion
(Neville and Brooks, 1999).

4.2 Control of Corrosion

Since water, oxygen, and chloride ions play important roles in the corrosion of
embedded steel and cracking of concrete, it is obvious that permeability of
concrete is the key to control the various processes involved in the phenomena.
Concrete mixture, to ensure low permeability, should have e.g., low water/cement
ratio, adequate cement, control of aggregate size and grading, and use of
mineral admixtures. In 1974 a study by British Building Research Establishment
showed that a sudden collapse of one main beam of a 12 –year old roof with post
tensioned pre-stressed concrete was due to corrosion of tendons (Mehta, 1999).
Poor grouting of ducts and the use of 2 to 4 percent calcium chloride by weight of
cement as an accelerating admixture in the concrete were diagnosed as the
factors responsible for the corrosion of concrete.According to British code of
practice 110 calcium chloride should never be added to prestressed concrete,
reinforced concrete , and concrete containing embedded metal. Reinforcing bar
coatings and cathodic protection provide other approaches to prevent corrosion
and are costlier than producing a low permeability concrete through quality,
design, and construction controls. Protective coatings for reinforcing steel are two
types anodic coatings (e.g., zinc-coated steel) and barrier coatings (e.g., epoxy-
coated steel). Cathodic protection techniques involve suppression of current flow
in the corrosion cell, either by supplying externally a current flow in the opposite
direction or by using sacrificial anodes.

5. CONCLUSIONS

It is important for the assessment of any cause of concrete deterioration to be

dependable. It should not be based on assumptions drawn from inconclusive
evidence, as the performance of materials in new construction, the reliability of
tests and the approach to the mitigation of the effects on structures will all be
based upon the diagnosis reached. This is especially the case with chemical
attack, which shares some characteristics with other mechanisms and may occur
in both harmless and damaging forms. Controlling the risk of concrete
deterioration by chemical attack may be achieved in number of ways i.e. by

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limiting the content of reactive alkalies, reduce water cement ratio and
permeability, use of admixtures, reducing chloride content.

REFERENCES

Mehta, P.K., and Paulo Monteiro, J.M., (1997), Concrete Micro Structure
Properties and Materials, Indian Edition, Indian Concrete Institute, Chennai,
pp.165-167.

Neville, A.M., and Brooks, J.J., (1999), Concrete Technology, International

Student Edition, Addison Wesley Longman, Inc., Harlow, U.K., pp. 275-276.

Rachel Detwiler, Guest Lecture on Alkali Silica Reaction at LMCC, 2003

Sharma Satish Kumar, and Keskar, S.B., (1997), “Factors Affecting Durability of
Concrete”, International Conference on Maintenance of Concrete Structures,
JNTU, Hyderabad.

Swenson, E.G., (1971), an Article on Concrete in Sulphate Environments, CBD-

136.