Durability of Concrete

Durability of Concrete
Topics discussed are

1)
2)
3)
4)
5)
6)
Permeability of concrete
Surface wear Erosion, Abrasion, Cavitation
Frost Action-Freezing and thawing Effects
Effect of fire
Thermal Properties of Concrete
Sulphate attack
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S.Praveenkumar
Assistant Professor
Department of Civil Engineering
PSG College of Technology
Coimbatore
Complied by
S.Praveenkumar/Assistant Professor/Department of Civil Engineering/PSGCT
Durability of Concrete
Sources:
Concrete Microstructure, Properties, and Materials - P Kumar Mehta and Paulo J M Monteiro
Advanced Concrete Technology - John Newman and Ban seng choo
Concrete Repair and Maintenance Peter H Emmons, Gahanna M Sabnis
Concrete Durability Thomas Dyer
1. Introduction
Designers of concrete structures have been mostly interested in the strength characteristics of the
material; for a variety of reasons, they must now become durability-conscious. Whereas properly
constituted, placed, and cured concrete can be durable under most natural and industrial
environments, cases of premature deterioration of concrete structures do occur and they provide
valuable lessons for control of factors responsible for the lack of durability.
Most concretes are excellent at 28 days. If not, a simple repair or replacement may be done.
However, concrete is meant to last for decades or centuries. After the first 28 days concrete will
continue to mature and age, depending on the original material composition and properties and
the environmental actions during service.
1.1.Definition
Along service life is considered synonymous with durability. As durability under one set of
conditions does not necessarily mean durability under another, it is customary to include a
general reference to the environment when defining durability. According to ACI Committee
201, durability of Portland cement concrete is defined as its ability to resist weathering action,
chemical attack, abrasion, or any other process of deterioration.
In other words, a durable concrete will retain its original form, quality, and serviceability when
exposed to its intended service environment. No material is inherently durable. As a result of
environmental interactions the microstructure and consequently the properties change with time.
A material is assumed to reach the end of service life when its properties, under given conditions
of use, have deteriorated to an extent that its continued use is ruled either unsafe or
uneconomical.
1.2.Durability Concept
Concrete may deteriorate with time in a number of ways. The most common durability failures in
an outdoor climate are due to reinforcement corrosion or frost attack. In special environments
concrete may suffer from chemical attack by various substances such as sulfates, acids, soft
water etc. causing disintegration or expansion. Durability failure may also occur because of
internal expansion from concrete constituents that are swelling, usually because of a reaction
product absorbing water.
The concept of durability is difficult to quantify. Durability may be good or better, but such
a description has no meaning without a proper definition. Additionally, durability is not a
property of a concrete material, or a concrete structure, but behavior, a performance, of a
concrete structure in a certain exposure condition. Service life is a much better concept for
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describing the durability of concrete. The service life is defined as the time during which a
concrete fulfils its performance requirements, without non-intended maintenance. Consequently,
service life is a quantitative concept, with the dimension [years] that can be compared for very
different alternative selection of materials or structural design concepts. To be able to define
service life, the performance of the concrete must be identified and the performance
requirements must be defined. Traditionally, the load-carrying capacity of a concrete structure is
taken as the design parameter, but from practice, experience shows that the performance could
involve a number of other things, i.e. aesthetics, apparent reliability, lack of visible signs of
deterioration, etc. The definition of service life is shown in Figure 1
Figure 1 Definition of Service Life

Service life design (SLD) is based on predictions of future deterioration. To be able to make a
design for service life certain information must be available:
Performance requirements; must be known, relevant and quantified.
Environmental conditions; decisive parameters must be known, including future changes.
Deterioration mechanisms; must be known; if not, the prediction methods, test methods and
properties will be irrelevant.
Prediction methods; preferably non-accelerated tests or, better, a theoretical model, decisive
material properties and environmental parameters.
Service life design in this way is carried out today mainly by considering initiation, and
propagation, of reinforcement corrosion.
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Permeability
In concrete, the role of water has to be seen in a proper perspective because, as a necessary
ingredient for the cement hydration reactions and as an agent that facilitates the mixing of the
components of concrete, water is present from the beginning. Gradually, depending on the
ambient conditions and the thickness of a concrete element, most of the evaporable water in
concrete (all the capillary water and a part of the adsorbed water) is lost, leaving the pores empty
or unsaturated. As it is the evaporable water that is freezable and also free for internal movement,
a concrete will not be vulnerable to water-related destructive phenomena if there is a little or no
evaporable water left after drying, and if subsequent exposure of that concrete to the
environment does not cause resaturation of the pores.
The latter, to a large extent, depends on the hydraulic conductivity, which is also known
as the coefficient of permeability (K). Note that, in concrete technology, it is a common practice
to drop the adjective and refer to K simply as the permeability.
Permeability is defined as the property that governs the rate of flow of a fluid into a
porous solid. For steady-state flow, the coefficient of permeability (K) is determined from
Darcys expression:
The coefficient of permeability of a concrete to gases and water vapor is much lower than the
coefficient for liquid water; therefore, tests for measurement of permeability are generally
carried out using water that has no dissolved air. Due to their interaction with cement paste, the
permeability values for solutions containing ions would be different from the water permeability.
Permeability of hardened cement paste
In hardened cement paste, at any point in time during the hydration process the size and
continuity of the pores would control the coefficient of permeability. The mixing water is
indirectly responsible for the permeability of hydrated cement paste because its content
determines, first, the total space and, subsequently, the unfilled space after the water has been
consumed either by cement hydration reactions or by evaporation to the environment. The
coefficient of permeability of freshly mixed cement paste is of the order of 104 to 105 cm/s;
with the progress of hydration, as the capillary porosity decreases, so does the coefficient of
permeability (Table 1), but there is no direct proportionality between the two. For instance, when
the capillary porosity decreases from 40 to 30 percent (Fig.1), the coefficient of permeability
drops by a much greater amount (i.e., from about 110 to 20 1012 cm/s).
However, a further decrease in the porosity from 30 to 20 percent brings about only a
small drop in permeability. This is because, in the beginning, as the cement hydration process
progresses, even a small decrease in the total capillary porosity is associated with considerable
segmentation of large pores, thus greatly reducing the size and number of channels of flow in the
cement paste. Typically, about 30 percent capillary porosity represent a point when the
interconnections between the pores have already become so tortuous that a further decrease in
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the porosity of the paste is not accompanied by a substantial decrease in the permeability
coefficient.
In general, when the water-cement ratio is high and the degree of hydration is low, the
cement paste will have a high capillary porosity. It will contain a relatively large number of big
and well-connected pores and, therefore, its coefficient of permeability will be high. As
hydration progresses, most of the pores will be reduced in size (e.g., 100 nm or less) and will
lose their interconnections and the permeability will drop. The coefficient of permeability of
cement paste when most of the capillary voids are small and not interconnected is of the order of
10 12 cm/s.
As stated, with conventional cement pastes the discontinuity in the capillary network is
generally reached when the capillary porosity is about 30 percent. With 0.4, 0.5, 0.6, and 0.7
water-cement ratio cement pastes this generally happens in 3, 14, 180, and 365 days of moist
curing, respectively. As the water-cement ratio in most concrete mixtures seldom exceeds 0.7,
theoretically, with most well-cured concrete mixtures, cement paste should not be the principal
contributing factor to the coefficient of permeability of concrete.
Table-1
Permeability of aggregate
Compared to 30 to 40 percent capillary porosity of ordinary cement paste present in hardened
concrete, the volume of pores in most natural aggregates is usually under 3 percent and rarely
exceeds 10 percent. It is expected, therefore, that the permeability of aggregate would be much
lower than that of the typical cement paste. However, this may not necessarily be the case. From
the permeability data of some natural rocks and cement pastes (Table 2), the coefficient of
permeability of aggregates are as variable as those of hydrated cement pastes of water-cement
ratios in the range 0.38 to 0.71. Although the coefficient of permeability of marble, trap rock,
diorite, basalt, and dense granite is generally of the order of 1 to 10 1012 cm/s, some varieties
of granite, limestone, sandstones, and cherts show values that are higher by two orders of
magnitude. The reason why some aggregates with only 10 percent porosity show much higher
permeability than the cement paste is that the size of capillary pores in aggregate is usually much
larger. Most of the capillaryporosity in a mature cement paste lies in the 10 to 100 nm range,
whereas the pore sizes in aggregate are, on the average, larger than 10 m. With some cherts and
limestone the pore size distribution involves a considerable content of fine pores. Their
permeability may be low, but such aggregates are vulnerable to expansion and cracking
associated with sluggish moisture movements and the resulting hydrostatic pressure.
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Permeability of concrete
Theoretically, the introduction of low-permeability aggregate particles into a high-permeability
cement paste (especially with high water-cement ratio pastes at early ages when the capillary
porosity is high) is expected to reduce the permeability of the system because the aggregate
particles should intercept the channels of flow within the cement paste matrix. Compared to a
neat cement paste, therefore, a mortar or a concrete with the same water-cement ratio and degree
of maturity should give a lower coefficient of permeability. Test data indicate that, in practice,
this does not happen. The two sets of data * in Fig. 2 clearly show that the addition of aggregate
to a cement paste or a mortar increased the permeability considerably; in fact, the larger the
aggregate size, the greater the coefficient of permeability. Typically, the permeability
coefficients for moderate- strength concrete (containing 38 mm aggregate, 356 kg/m3 cement,
and an 0.5 water-cement ratio), and low-strength concrete used in dams (75 to 150 mm
aggregate, 148 kg/m3 cement, and an 0.75 water-cement ratio) are of the order of 1 1010 and
30 1010 cm/s, respectively.
Why the permeability of mortar or concrete is higher than the permeability of the
corresponding cement paste?
The explanation as to why the permeability of mortar or concrete is higher than the
permeability of the corresponding cement paste lies in the microcracks normally present
in the interfacial transition zone between aggregate and the cement paste.
The aggregate size and grading affect the bleeding characteristic of a concrete mixture
that, in turn, influences the interfacial transition zone.
During the early hydration period the interfacial transition zone is weak and vulnerable to
cracking from differential strains between the cement paste and the aggregate particles
that are induced by drying shrinkage, thermal shrinkage, and externally applied load.
The cracks in the interfacial transition zone are too small to be seen by the naked eye, but
are larger than most capillary cavities present in the cement paste matrix.
Later, the propagation of microcracks establishes the interconnections that become
instrumental in increasing the permeability of the system.
Due to the significance of the permeability to physical and chemical processes of
deterioration of concrete, a brief review of the factor controlling the permeability of
concrete should be useful.
Because strength and permeability are related to each other through the capillary porosity
(Fig.3), as a first approximation the factors that influence the strength of concrete (Fig.4) also
influence the permeability.
A reduction in the volume of large (e.g., >100 nm) capillary voids in the paste matrix
will reduce the permeability. This should be possible by using a low water-cement ratio,
adequate cement content, and proper compaction and curing.
Similarly, proper attention to the aggregate size and grading, thermal and drying
shrinkage strains, and premature or excessive loading are necessary steps to reduce micro
cracking in the interfacial transition zone, which is the major cause of high permeability of
concrete infield practice. Finally, it should also be noted that tortuosity of the path of fluid flow
that determines the permeability also depends on the thickness of the concrete member. The
permeability coefficient in SI units is expressed as kg/Pa.m.s, which is an approximately 103
time smaller than the coefficient expressed in cm/s.
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Figure-3
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Figure-4
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Surface wear
Progressive loss of mass from a concrete surface can occur due to abrasion, erosion, and
cavitation.
The term abrasion generally refers to dry attrition, such as in the case of wear on
pavements and industrial floors by vehicular traffic.
The term erosion is normally used to describe wear by the abrasive action of fluids
containing solid particles in suspension. Erosion takes place in hydraulic structures, for
instance canal linings, spillways, and concrete pipes for water or sewage transport.
Another possibility of damage to hydraulic structures is by cavitation, which relates to
loss of mass by formation of vapor bubbles and their subsequent collapse due to sudden
change of direction in rapidly flowing water.
Mechanism of abrasion and erosion
The term abrasion covers a wide range of processes acting on a concrete surface to cause it to
progressively lose material. In general terms, we normally think of abrasion as being the action
of sandpaper on a surface one solid surface slides over another, with one of the surfaces (the
sandpaper) being harder and consequently removing a proportion of the softer surface. From
experience, we know that we must also apply some pressure to the sandpaper there must be a
force acting to push the surfaces together at right angles to the direction of movement. The
aforementioned process is indeed one of the mechanisms that cause abrasion of concrete surfaces
(Figure 6). It is referred to as abrasion by friction and is one of the main processes occurring
during erosion, caused by particles being carried over a concrete surface by water.
However, the same effect can be caused by skidding of a wheel or foot on a pavement or
floor surface. Moreover, debris, such as dust and grit, between the wheel or foot and the concrete
surface will also have a similar and potentially more damaging effect. Moving particles may also
abrade a surface by simply impacting with it head-on (Figure 7).
Impacts of this type can cause fragments to break free from the surface or initiate surface
cracks that may grow to produce fragmentation after a period of time. Of course, interactions
between moving particles and concrete surfaces need not be at either of these extremes, and
impacts can have angles of incidence between 90 and very low angles, with a combination of
friction and impact abrasion occurring with each particle strike.
Figure-6
Figure-7
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Abrasion is the wearing away of the surface by rubbing and friction. Generally, the surface is
uniformly worn away, including the cement matrix and aggregates. Factors affecting abrasion
resistance include
1. Compressive strength
2. Aggregate properties
3. Finishing methods
4. Use of toppings
5. Curing
Figure-8
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Erosion
Figure-9 shows the effect of two different angles of incidence (15 and 90) on the rate of
abrasion of a concrete surface with the higher angle being more damaging. The figure also
illustrates the influence of another factor that influences erosion rates fluid velocity with
higher velocities producing greater rates of erosion. Other factors that influence the rate of
erosion are the mass of particles carried in a suspension, particle size, shape, and hardness.
Figure-10 illustrates the effect of the quantity of particles, with an increase in the concentration
of particles producing faster erosion. Typically, larger particles travelling at a given velocity will
produce a larger rate of abrasion.
Particle size is related to fluid velocity, since a higher velocity will allow moving water
to carry larger articles. The influence of particle shape on erosion rates appears dependent on the
angle of incidence, with angular particles causing erosion at slightly lower rates compared with
rounded particles at low angles, but causing erosion at much greater rates at 90.
It has been proposed that this is because at 90, angular particles striking the surface will
be more effective at inducing cracking in particles of aggregate in the concrete, since their sharp
corners will apply higher stresses during impact. At low angles, the manner in which the angular
particles strike the concrete is such that this concentration of stress is less likely to occur.
The rate of erosion increases with the hardness of the particles carried by a fluid.
Cavitation
Cavitation causes erosion of concrete surfaces resulting from the collapse of vapor bubbles
formed by pressure changes within a high velocity water flow. When vapor bubbles form, they
flow downstream with the water. When they enter a region of higher pressure, they collapse
(implode) with great impact. The formation of vapor bubbles and their subsequent collapse is
called cavitation. The energy released upon their collapse causes cavitation damage. Cavitation
damage results in the erosion of the cement matrix, leaving harder aggregate in place. At higher
velocities, the forces of cavitation may be great enough to wear away large quantities of
concrete. The bubbles of water vapour violently collapse in a manner similar to that shown in
Figure 11. This collapse produces a fast-moving jet of water that leads to the generation of
significant local stresses. It is these stresses that, when they occur against a concrete surface,
produce damage. Generally speaking, damage can start where the cavitation index exceeds a
value of 0.2.Figure-12 shows Cavitation damage is avoided by producing smooth surfaces and
avoiding protruding obstructions to flow.
Damage from individual cavitation events takes the form of small pits in the surface, but since
the formation of bubbles will typically occur with great frequency, the cumulative effect can be
significant. Generally, accumulation of damage is initially slow, but increases with time until the
rate of loss of material peaks and declines. The action of traffic over a concrete surface will also
generate stresses that can cause microcracking, ultimately leading to abrasion.
Figure-13 shows the different stresses that take the form of vertical compressive stresses,
horizontal tensile and compressive stresses and shear stresses. The relatively low strength of
concrete in tension and shear makes these types of stress the largest threat to the integrity of a
pavement or floor, although large vehicles will induce significant compressive strengths.
Although the diagram shows a wheel, it is clear that the action of a human foot will produce
similar stress distributions, albeit of a smaller magnitude.
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Figure-9
Figure-10
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Figure-11
Figure-12
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Figure-13
Factors Influencing resistance to Abrasion & Erosion
When considering the results of research into the variables that influence abrasion and erosion
resistance of concrete, it is important to note that this can be measured using a wide variety of
tests. Specifically, the manner in which abrasive action is achieved varies considerably, and it is
important to stress that, although in most instances a similar behaviour is likely to be observed
regardless of the test being used, cases have been reported where this is not the case.
ASTM C779 addresses abrasion of horizontal concrete surfaces. The standard describes three
different techniques.
The first two techniques involve a test machine consisting of a revolving carousel that is
able to apply a constant load to the surface that is being tested. In the first test, the load is applied
through three revolving steel discs. The rate of the revolution of both the carousel and the discs is
defined in the standard. The carousel is run for a period of 30 or 60 min depending on whether
long-term performance is a key concern. The machine feeds abrasive silicon carbide grit, which
is fed onto the test surface at a constant defined rate. Abrasion resistance is evaluated by
measuring the depth of wear at the end of the test.
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The second of the horizontal surface tests does not use grit, and the revolving discs are
replaced by three dressing wheelsspiked steel rollers that travel over the concrete surface.
Again, after the machine is run for anperiod of either 30 or 60 min, depth of wear measurements
are taken.
The third test uses a different type of machine that consists of a revolving hollow drive
shaft that applies a constant load to a ring containing a series of captive, but freely moving, ball
bearings held against the concrete surface. The drive shaft is revolved at a defined rate, and the
depth of wear is measured using a micrometer gauge that is part of the apparatus. The abrasion
resistance is expressed in terms of the time required to reach a specified depth of wear.
There are additionally two ASTM tests for concrete resistance to erosion type processes.
The first of these, ASTM C418, uses sandblasting in a cabinet using a standardized gun
nozzle and a standardized abrasive delivered onto the surface of a concrete specimen at a
specified rate under a specified pressure for 1 min. The rate of abrasion is estimated by
measuring the mean volume of the cavities produced on a number of spots by determining the
mass of plastic clay of known density required to fill the cavity.
The second method, ASTM 1138M , is the underwater method and attempts to more
closely mimic the conditions encountered when concrete is exposed to sediment carried by
moving water. In the method, the cylindrical concrete specimen is placed in a cylindrical tank,
with the surface to be tested facing upward. Steel balls of various sizes are placed on the surface,
and the tank is filled with water. A paddle of specified dimensions and geometry is submerged in
the water at a fixed distance above the concrete surface and rotated at a speed of 1200
revolutions per minute. The concrete specimen is periodically removed and weighed to
determine the loss of mass resulting from abrasion up to a test age of 72 h.
Because abrasion is purely mechanical process acting on the surface of the concrete, it is not
surprising that strength plays a very important role in defining the resistance of concrete to this
mode of deterioration.
1) The strength of both the aggregate and the cement matrix plays a role, and the importance
of these properties is very much dependent on whether the cement matrix or the
aggregate is the stronger material.
2) The influence of cement content on abrasion resistance is dependent on the strength of
the cement matrix.
3) With very low W/C ratios, where the strength of the paste is higher than that of the
aggregate, increases in resistance with an increase in cement content are observed (for a
fixed W/C ratio). However, the opposite is true where the strength of the concrete is
lower than the aggregate.
4) Stronger aggregate will typically produce greater resistance to abrasion. However, this
effect is more pronounced where the strength of the concrete is lower.
5) Maximum aggregate size appears to be important, with a larger value producing greater
resistance.
6) It should be stressed that since normal mix design techniques reduce the cement content
as maximum aggregate size increases, this factor may have an influence on experimental
results.
7) Nonetheless, when the proportion of coarse aggregate is reduced, there is an increase in
abrasion resistance, indicating that aggregate size has a genuine influence.
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8) As with most durability characteristics, adequate curing of concrete is of great

importance.
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Frost action (Freezing and thawing attack)

Water is one of a very limited number of substances that undergoes an increase in volume when
it transforms from a liquid to a solid. Within the confines of the pores of concrete, this expansion
can lead to damage over repeated cycles of freezing and thawing.
Volume changes of water
Figure 14 shows the density of water and ice over a range of temperatures. The density of liquid
water at 0C is approximately 1000 kg/m3,whereas the density of ice at the same temperature is
917 kg/m3, resulting in an increase in volume during freezing of approximately 9%. It should be
noted that water may persist in the liquid state below 0C if it is supercooled. Supercooling can
occur for a number of reasons, the most common of which being that the water is not
mechanically agitated during cooling.
Figure-14
Action of Ice Formation in Concrete
Free water in concrete is confined within pores. Freezing of this water leads to expansion, which,
within the confined space of the pores, causes the development of stresses that can lead to
cracking. However, cracking may occur in concrete whose pore system is not fully saturated. To
understand why this is, it is necessary to look at the process of freezing in concrete in more
detail.
Water in concrete pores does not freeze at 0C. There are two main reasons for this. First,
the freezing point of water is depressed by the presence of dissolved ions. Second, the adsorption
of water on pore surfaces has the effect of permitting the supercooling of water.
The overall effect of this is that freezing of free water in concrete does not occur at a
single temperature. Instead, solidification occurs progressively over a temperature range, with
water in large pores crystallizing first. In larger pores, where the ratio of the pore wall surface to
the pore volume is relatively small, freezing occurs at relatively high temperatures. However, in
small pores, where the adsorbed layer of water is almost as thick as the pore radius, freezing will
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not occur potentially until temperatures lower than those experienced under terrestrial ambient
conditions are reached.
The combination of the formation of a less dense solid and the persistence of a layer of liquid
leads to the liquid exerting a hydraulic pressure. Although several mechanisms for how the
concrete is damaged have been proposed, the most widely accepted explanation is that the flow
of water away from areas of freezing leads to viscous resistance against water movement.
This produces hydraulic pressures within the pores, which may be enough to cause tensile
cracking. This resistance to flow is proportional to the length of the flow path of water in the
pores, and the pressure developed (P, in N/m2) is described through a rearrangement of the
conventional equation for Darcys law:
where Q is the flow rate of water (m/s), L is the length of the flow path (m), is the viscosity of
water (Ns/m2) and k is the permeability of the flow path(m2) As well as damage to the concrete,
the pore will undergo permanent deformation. This deformation creates additional pore space,
which is subsequently filled with water when the concrete next becomes saturated. Thus,
multiple freezethaw cycles lead to progressive damage to the concrete, as illustrated in Figure15
Figure-15
Both the cement matrix and the aggregate can potentially undergo damage as a result of freeze
thaw attack, with the behaviour of these different components defining the manner in which
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deterioration occurs. Thus, the damage produced as a result of cyclic freezing and thawing can
vary and can include scaling, D-cracking and pop-outs.
a) Scaling
Scaling is the loss of material from the concrete surface (Figure 16). Since scaling involves the
loss of surface; it results in a loss in the cross-sectional area and a loss of cover. Scaling is often
particularly problematic where other types of mechanical action are effective on the concrete
surface. The nature of the surface of the concrete will influence its susceptibility to scaling. The
surface contains a higher proportion of cement paste, which tends to be prone to delamination
from the aggregate-rich material beneath it once the tensile strength of the bond between the two
materials is exceeded by the action of ice formation.
The presence of de-icing compounds can have the effect of increasing the rate of scaling.
This is largely the result of the osmotic pressures discussed above, because the presence of deicing salts will considerably increase the amount of dissolved species in the pore solution.
Several compounds can be used for de-icing, and it has been proposed that the extent to which
scaling is exacerbated by their presence follows the approximate sequence ammonium nitrate =
ammonium sulphate potassium chloride urea magnesium chloride calcium chloride
sodium chloride .
In addition to these compounds, ethylene glycol, propylene glycol, potassium acetate and
calciummagnesium acetate are also used as de-icers. For scaling to occur, it is necessary for a
pool of solution to be present at the concrete surface and for the minimum temperature reached
to be less than 10C. Additionally, the rate of scaling is dependent on the concentration of the
de-icer present in the solution, with the fastest rate of deterioration occurring around a
pessimum concentration of around 3% by mass, seemingly regardless of what de-icer is used.
b) D-Cracking
D-cracking results from the fragmentation of aggregates rather than of cement paste. It
frequently occurs in slabs and is observed at the surface in the form of cracks close to edges and
joints (Figure 17).
The process of D-cracking usually initiates where the concrete (and more specifically the
aggregate in the concrete) is saturated above a critical level. In pavement slabs, this typically
occurs at the base, where the concrete is potentially in contact with water-bearing road-base and
subbase layers.
Only certain aggregate sources are prone to freezethaw deterioration, and test methods exist for
evaluating susceptibility. In general terms, susceptibility is dependent on the pore structure of
aggregates. Specifically, freezethaw resistance is determined by the volume of porosity within
the aggregate particles, the pore size, and the length of flow paths running through the particles.
The influence of the first two of these parameters has been characterized in the form of the
equation
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Where EDF is the expected durability factor, P is the pore volume down to a pore diameter of
4.5 m (cm3/g), Dmedian is the median pore diameter down to a pore diameter of 4.5 m (m) and
K1, K2, and K3 are constants
The durability factor referred to in the equation is a factor that can be calculated from
fundamental frequency measurements made on concrete specimens exposed to freezethaw
cycles, as defined in ASTM C-666 .
It is defined as
Where DF is the durability factor, n1 is the fundamental frequency of the concrete specimen at 0
cycles, n is the fundamental frequency at N cycles, N is the number of cycles at which (n12/ n2)
reaches a specified minimum value or the specified number of cycles at which exposure is to be
terminated, whichever is less and M is the specified number of cycles at which exposure is to be
terminated. A high durability factor represents a high resistance to freezethaw attack. Thus, a
low volume of total porosity and coarser pore sizes will give a higher resistance to freezethaw
attack. It has been proposed that values for K1, K2, and K3 of 0.579, 6.12, and 3.04, respectively,
are appropriate and that an EDF below 40 indicates susceptibility to D-cracking. The reason for
the exclusion of pore diameters below 4.5 m relates to the suppression of freezing points in
pores, since water in pores smaller than this is unlikely to freeze under terrestrial ambient
temperatures.
The reason for the flow path length playing a role in influencing the freezethaw durability of
aggregate is the same as discussed previously for cement paste. However, for aggregate, it has a
different significance: since the flow path length will be limited by aggregate size, coarser
aggregate is more susceptible to freezethaw damage.
Lightweight aggregates can potentially be susceptible to freezethaw attack, since they can
accommodate large volumes of water. Generally speaking, the lower the density of lightweight
aggregate, the more susceptible it will be. However, as for normal-weight aggregate, pore
structure is an important factor, with smaller pore size distributions giving greater resistance.
c) Pop-outs
Pop-outs are also the result of aggregate susceptibility to freezethaw attack. In this case,
damage occurs as a result of the expansion of aggregate particles close to the surface, leading to
surface cracking and the loss of small conical volumes of mortar at the surface around the
aggregate particle, as shown in Figure 18.
Figure-16
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Figure-17
Figure-18
Freeze Thaw Disintegration

Freeze-thaw disintegration or deterioration takes place when the following conditions are
present:
1. Freezing and thawing temperature cycles within the concrete.
2. Porous concrete that absorbs water (water-filled pores and capillaries)
Freeze thaw deterioration generally occurs on horizontal surfaces that are exposed to water, or on
vertical surfaces that are at the water line in submerged portions of structures. The freezing water
contained in the pore structure expands as it is converted into ice. The expansion causes localized
tension forces that fracture the surrounding concrete matrix. The fracturing occurs in small
pieces, working from the outer surfaces inward.
The rate of freeze-thaw deterioration is a function of the following:
1. Increased porosity ( increases rate)
2. Increased moisture saturation (increases rate)
3. Increased number of freeze thaw cycles (increases rate)
4. Air entrainment (reduces rate)
5. Horizontal surfaces that trap standing water (increases rate)
6. Aggregate with small capacity structure and high absorption (increases rate)
Figure-19 shows the freeze thaw disintegration mechanisms
Factors affecting the frost resistance of concrete
The ability of a concrete to resist damage due to frost action depends on the characteristics of
both the cement paste and the aggregate. In each case, however, the outcome is controlled
actually by the interaction of several factors, such as the location of escape boundaries (the
distance by which water has to travel for pressure relief), the pore structure of the system (size,
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Figure-19
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Number, and continuity of pores), the degree of saturation (amount of freezable water present),
the rate of cooling, and the tensile strength of the material that must be exceeded to cause
rupture. The provision of escape boundaries in the cement paste matrix and modification of its
pore structure are the two parameters that are relatively easy to control; the former can be
controlled by means of air entrainment in concrete and the latter by the use of proper mix
proportions and curing.
The key factors are
1) Air entrainment
2) Water cement ratio and curing
3) Degree of saturation
4) Strength
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Effect of fire
Concrete is generally considered to perform well when exposed to fire since it is inorganic, noncombustible and does not give off noxious fumes. Moreover, as well as being noncombustible,
concrete is a poor conductor of heat and has a relatively high specific heat capacity, which
facilitates its use as a protection material to other elements and even as a heat storage medium.
There are, however, several issues that make the real behavior of concretes in fire conditions less
straightforward and these are related to compositional and phase changes within concrete
constituents and the behavior of absorbed moisture.
Concrete as a material, it is difficult to discuss this meaningfully without considering the
manner of its incorporation in structures and the temperature response of steel, either because of
the use of concrete with embedded steel reinforcement or because concrete is used to provide fire
protection for steel structures.
Essentials of Concrete Behavior
There are two principal effects of fires on structural concrete:
Loss in strength of matrix by degradation of hydrate structure. This occurs at various stages
from 300C upwards but the main losses are seen at 500C plus.
Spalling and shelling of the outermost concrete. This can occur with most concretes but the
extent and rate is influenced by aggregate type, moisture content, concrete quality, fire severity
and imposed stress condition.
The overall behavior of concrete in a fire is the result of the complex interaction of the
mechanisms of strength loss and spalling. Although there has been considerable research on
concrete in fires and individual mechanisms identified and understood, the complexity of the
interactions makes precise prediction of behavior of concrete in structures extremely difficult.
Fire Damage
Fire affects concrete in extreme ways, some of which are listed below:
1. Uneven volume changes in affected members, resulting in distortion, buckling and
cracking. The temperature gradients are extreme: from ambient 21C, to higher than
800C at the source of the fire and near the surface.
2. Spalling of rapidly expanding concrete surface from extreme heat near the source of the
fire. Some aggregates expand in bursts, spalling the adjacent matrix. Moisture rapidly
changes to steam, causing localized bursting of small pieces of concrete.
3. The cement mortar converts to quicklime at temperatures of 400C, thereby causing
disintegration of the concrete.
4. Reinforcing steel loses tensile capacity as the temperature rises.
5. Once the reinforcing steel is exposed by the spalling action, the steel expands more
rapidly than the surrounding concrete, causing buckling and loss of bond to adjacent
concrete where the reinforcement is fully encased.
Figure-20 shows the effect of fire in structure.
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Strength loss in the cement matrix

Strength loss in the concrete matrix has been researched but some divergences in the detailed
conclusions are found in references. While individual mechanisms can be identified in specific
matrix components, e.g. the breakdown of hydrates in any one type of cement, the variety of
processes creating change in materials properties and their interactions result in different specific
values and consequences from the different researches. The broad temperature ranges over which
the changes occur and their effects on concrete properties, discussed below, should, however, be
sufficient to estimate overall performance and evaluate damage.
On initial heating concrete will first lose absorbed, free or evaporable water then bound
or adsorbed water. This loss of water may induce microcracking and some consequent loss in
compressive strength, possibly up to 10%. From 150C upwards some degradation loss of water
from silicate hydrates and from Portlandite (calcium hydroxide) can occur but above 300C the
loss of bound water from the hydration products becomes more prominent and further strength
loss will occur. With increasing temperature the strength loss continues in the silicate hydrates
and, at 350400C, in the calcium hydroxide by dehydration to form calcium oxide. It is also
suggested that the formation of calcium oxide can result in post-fire damage should the calcium
oxide react with water, such as from fire extinguishing efforts, causing swelling and cracking. By
approximately 500C a considerable loss in strength has occurred variously recorded as 50 to
75% of original strength and temperatures in the range 550600C have variously been taken
as the upper limit for retention of any useful strength in the concrete. However, degradation
processes and losses continue to take place up to 850900C. The strength loss does not appear
to be uniquely defined and research outputs vary in the extent of loss recorded, but reductions of
the order of 7080% are quoted where the concrete becomes loose and friable.
A similar scale of change is found in concrete compressive modulus, over the same
temperature ranges described above in relation to strength. The type of cement is thought to have
some influence on strength loss. For cements with fly ash or ground granulated blast furnace slag
there is some suggestion that the lower quantities of free calcium hydroxide in the hydrated
microstructure give reduced losses on heating. However, for most Portland type cements, these
differences are sufficiently small as to not affect the practical performance of the concrete and
therefore cement types are not explicitly selected for fire resistance.
There are two exceptions to this general conclusion on cement type. The first is concretes
with microsilica where the very low permeability paste produced is thought to significantly
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Figure-20
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increases spalling risk see below on high strength concrete. The second exception is concrete
made with Calcium aluminate cements. These have greater resistance to strength loss at high
temperatures and are used for specialist non-structural applications such as refractory linings or
industrial floor toppings in foundries
Spalling
Spalling of concrete in fires is the breaking-off of layers of the concrete surface in response to
the applied heat. Spalling can be either localized or widespread depending upon the fire and/or
concrete condition, particularly moisture content, and the susceptibility to break-up of heatunstable aggregate particles. On prolonged heating areas of concrete cover can also just fall
away, a process that is sometimes called sloughing. The processes causing sloughing are not
generally reported, although it is noted that it occurs from corners of beams and slabs and seems
to spread along a plane of weakness parallel to the outer surface. Because sloughing occurs late
in a fire exposure it is considered by some as being of less concern than explosive spalling that
occurs earlier upon exposure to fire. Understanding explosive spalling is important because of
the potential for loss in section of the concrete element, the depth of fire affected concrete and
the reduced protection to embedded steel. Spalling is a frequently observed phenomenon in fire;
more prominently on soffits of slabs and on beams because of the greater exposure to heat and
possibly heat entrapment.
The prediction of risk of spalling occurrence has not proven easy despite considerable
research. The propensity to spall is influenced by the moisture content of the concrete, the
permeability of the concrete, the rate of heating, the nature of the aggregate and the load applied
to the concrete. Although these separate contributing mechanisms have been identified, their
relative contribution and their interaction are less well understood. There are, however, general
trends that can be established. Concretes in a moist or saturated condition will spall faster and
more extensively the drier the concrete.
Influence of Aggregate type
The contribution of aggregate type to spalling and section loss is both from the nature of the
aggregate itself and the differences in temperature-related properties between aggregates and the
surrounding matrix. It is commonly found that siliceous aggregates such as flint gravels give the
poorest resistance to spalling. This is explained by being partly the result of markedly different
coefficients of thermal expansion between the aggregate and cement paste, particularly at higher
temperatures, and partly the result of a volume increase phase transformation (at approximately
570C) from -quartz to -quartz.
Limestone aggregates have generally been shown to give good fire resisting performance
but not all design codes have found the evidence consistent enough to give design guidance
differentiating that performance. There are several reasons why limestone type aggregates can be
expected to give improved resistance to degradation. First, the aggregates typically have lower
coefficient of thermal expansion than siliceous aggregates and they are closer to that of cement
paste, giving lower internal stresses on heating. There are also no solid state phase changes in
limestone aggregates within fire exposure conditions. On heating to temperatures in excess of
660C calcium carbonates begin to break down, similarly above 740C for magnesium
carbonates. On breaking down the minerals release carbon dioxide, in itself an endothermic
reaction, but the released carbon dioxide is claimed to give blanketing protection against heat
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transfer. The residual aggregate particles also have lower thermal conductivity, further reducing
heat transfer into the concrete.
Behavior of Concrete in Extreme fires
Concrete does not melt in the majority of extreme fire conditions but it could do so in
conditions such as created by, for example, a thermic lance (steel burning in a pure oxygen
environment). However, this is exceptional and is not normally considered in the design of
reinforced concrete subject to hydrocarbon fires.
Rapid heat rise in concrete causes evaporation of free and physically bound water and, at higher
temperatures, moisture loss by dehydration of cement hydrates. If the permeability of the
concrete is insufficient to allow an adequate rate of dissipation then the vapour pressure in the
pores of the concrete will rise. A contribution to the low apparent permeability-resisting vapour
dissipation is the vapour condensation further inside the concrete away from the fire. Once the
vapour pressure rises to a critical level cracking and explosive spalling will occur.
This explosive spalling can occur after only a few minutes and rates are quoted in some
reports of up to 3 mm/min for normal-weight aggregate concrete and up to 8 mm/ min for
lightweight aggregate concrete. More information is needed on these rates and the contribution
from the various parameters.
Other types of spalling such as local spalling and sloughing-off (gradual reduction of a
cross-section) that have been observed in cellulosic fires are possible but explosive spalling
seems to be the dominant form in an extreme hydrocarbon fire.
As was described earlier, concrete subjected to high temperature will suffer loss of
strength. The strength loss increases as the temperature increases and both the aggregate and the
cement hydrates are affected. At the very high peak temperatures in a hydrocarbon fire the
aggregate and cement hydrates may be completely destroyed. Many factors have an influence on
the performance of concrete in hydrocarbon fire but those with a primary influence are:
o the rate of temperature rise in the concrete
o the moisture content of the concrete
o the permeability of the concrete
These factors are interlinked but there is some evidence to suggest that, at least for low
permeability concrete, sufficient vapour pressure for damage to occur can be generated by
decomposition of cement hydration products alone, even where there is little or no free water
within the concrete pores. This would mean that indoor concrete would never dry sufficiently for
spalling not to be a problem and, that self-desiccation in concrete with a very low water/cement
ratio would not alleviate the problem.
The definition of satisfactory performance will be dependent on individual
circumstances. Nevertheless, it is likely that the very high rate of temperature rise in a
hydrocarbon fire will cause explosive spalling and loss of section at a high rate, particularly in
high strength concrete and lightweight aggregate concrete. Reinforcement could thus be exposed
to high temperatures in less than approximately 20 minutes depending on depth of cover and
other factors.
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Improving the Fire Resistance of Concrete

For many fire incidents concrete can be considered to be sufficiently resistant to damage by fire
that, on its own, it needs no further protection. There may, however, be situations where more
severe design fires are envisaged, or the existing concrete construction is considered inadequate
for new conditions or where concern about the inherent performance exist, e.g. for high-strength
concrete. For these conditions enhanced fire protection or resistance may be required.
Where a simple increase in the thickness of concrete cover would satisfy the design
requirements, the design Codes allow the use of equivalent thicknesses of other passive materials
such as sand cement render or gypsum plaster. Alternatively, fire protection boards can be
mechanically fixed around the concrete sections. Steel structures are frequently protected against
fire by the application of relatively thin intumescent coatings, which foam upon exposure to
produce a protective char. Although attempts have been made to use these materials on concrete,
they have not been very successful to date. One particular problem is that, even with the
protection in place, the temperature in the concrete is sufficient to vaporize moisture which then
disrupts the coating.
One method for improving the fire performance of high strength concrete in cellulosic
fires and all types of concrete in more extreme fires, is the incorporation of fine polypropylene
fibres within the concrete (HSE, 2001). At present this route is only adopted for new concretes
where the fibres can be incorporated into the mix but it may be possible to develop overlays for
some existing structures. The action of polypropylene fibres was initially believed to be by fibre
melting and vaporization upon heating providing escape pathways for moisture. It was known
from tests that such fibres could be effective but not all fibres were found to be equally effective
and there was some uncertainty about the influence of fibre geometry and quantity. Research in
France (Kalifa et al., 2001) has provided significantly better insight into the mechanism of
beneficial action by the fibres.
The research measured the pressure build-up in the porous network within the concrete
for additions of different polypropylene fibres close to the conventional level of approximately
2 kg/m3. The data obtained showed that lower dosages than previously thought can be beneficial
and that the fibres are already contributing to preventative action at temperatures well below that
necessary for vaporization. It was concluded that the polypropylene on melting at
approximately 170C was absorbed into the cement paste of the matrix, creating the necessary
pathways. Further research on this aspect would be helpful in increasing understanding.
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Thermal Properties of Concrete

Generally, thermal properties of concrete are to understand the behavior of concrete to heating
and cooling. The study of thermal properties of concrete is an important aspect while dealing
with the durability of concrete.
Concrete is a material used in all climatic regions for all kinds of structures. Knowledge
of thermal expansion is required in long span bridge girders, high rise buildings subjected to
variation of temperatures, in calculating thermal strain in chimneys, blast furnace and pressure
vessels, in dealing with pavements and construction joints, in dealing with design of concrete
dams and in host of other structures where concrete will be subjected to higher temperatures such
as fire, subsequent cooling, resulting in cracks, loss of serviceability and durability.
The important properties that will be discussed are:
Thermal conductivity
Thermal diffusivity
Specific heat
Coefficient of thermal expansion
Thermal conductivity- This measures the ability of material to conduct heat. Thermal
conductivity is measured in joules per second per square metre of area of body when the
temperature deference is 1C per metre thickness of the body.
The conductivity of concrete depends on the type of aggregate, moisture content, density,
and temperature of concrete. When concrete is saturated, the conductivity ranges generally
between 1.4 and 3.4 j/m2sc/m.
Thermal diffusivity- Diffusivity represents the rate at which temperature changes within the
concrete mass. Diffusivity is simply related to the conductivity by the following equation.
Diffusivity=
The range of diffusivity of concrete is between 0.002 to 0.006 m2/h

Specific heat- It is defined as the quantity of heat required to raise temperature of a unit mass of
a material by one degree centigrade. The common range of values for concrete is between 840
and 1170 j/kg perc.
Coefficient of thermal expansion-Coefficient of thermal expansion is defined as the change in
unit length per degree change of temperature. In concrete it depends upon the mix proportions.
The coefficient of thermal expansion of hydrated cement paste varies between 11 x 10-6 and 20 x
10-6 per C. Coefficient of thermal expansion of aggregates varies between 5 x 10-6 and 12 x 10-6
per C. Limestones and gabbros will have low values and gravel and quartzite will have high
values of coefficient of thermal expansion. Therefore the kind of aggregate and content of
aggregate influences the coefficient of thermal expansion of concrete.
Too much of thermal incompatibility between aggregate and paste, causes differential
expansion and contraction resulting in rupture of bond at the interface of paste and aggregate.
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Concrete subjected to higher temperatures show somewhat different values, presumably because
of the lower moisture content in the concrete. The importance of the values of coefficient of
thermal expansion becomes necessary at higher temperature when dealing with concrete
subjected fire or higher temperatures.
Having seen a few aspects of properties of concrete which have bearing on expansion and
contraction on heating and cooling, let us revert back to thermal shrinkage associated with heat
of hydration.
A large amount of heat, up to 500 j/g could be liberated in the hydration of cement. Since
the thermal conductivity of concrete is low, a very high temperature could be generated in the
interior of a large mass of concrete. At the same time, the exterior of the concrete mass loses heat
with the result a steep temperature gradient may get established. During subsequent cooling of
the interior, serious cracking may take place.
The rate of evolution of heat as well as total generated depends on the compound
composition of cement. C3S and C3A produces large amount of heat in a short time. The fineness
of cement also influences the rate of heat development. The faster rate of heat development is
more harmful than the total heat of hydration which develops slowly. Therefore for mass
concrete and hydraulic structures they use cement with low C3S and C3A. It is also advantages to
use low cement content and blended cement. Blended cement with high pozzolanic materials
content gives out the heat rather slowly because of slow pozzolanic reaction, during which time
certain quantity of heat gas dissipated, virtually reducing temperature difference between interior
and exterior.
Thermal Effects
The effect of temperature on concrete structures and members is one of the volume changes. The
volume relationship to temperature is expressed by the coefficient of thermal
expansion/contraction. Volume changes create stress when the concrete is restrained, the
resulting stresses can be of any type: tension, compression, shear etc. the stressed conditions may
result in undesirable behavior such as cracking, spalling, and excessive deflection.
a) Thermal volume change
Concrete, like all materials, changes volume when subjected to temperature changes. An increase
in temperature increases the volume of concrete; conversely, a decrease in temperature reduces
the volume of concrete. The thermal coefficient is 9 x 10-6 mm/mm/C. Example: A Change of
38C (100F) in a 30.5m (100) length will length will change the overall length by 22mm
(7/8).
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b) Uneven Thermal Loads

Temperature gradients exist in many structures. The temperature on the surface of a deck
slab exposed to direct sunlight may reach 48C (118F), while the underside of the deck may
be only 26C-22C (78F-40F) difference known as diurnal solar beating. This causes the
top surface to have a tendency to expand more than the bottom surface. This results in an
upward movement during heating and a downward movement during cooling.
Example: A precast double T-shaped structured member with 18m span can move 19mm
upward at mid span from normal diurnal solar heating, causing the ends to rotate and stress
the ledger beam bearing pads and concrete.
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c) Continuous span
Diurnal solar heating affects structures differently depending upon their configuration. Simple
span structures deflect up and down and are free to rotate at end supports. Continuous structures
may behave differently because they are not free to rotate at supports. If enough thermal
gradients exist, together with insufficient tensile capacity in the bottom of the member, a hinge
may form. Hinges may occur randomly in newly formed cracks, or may form in construction
joints near the columns. Hinges open and close with daily temperature changes.
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d) Restraint volume changes

If a structural member is free to deform as a result of changes in temperature, moisture, or loads,
there is no build-up of internal stress. If the structural member is restrained, stress build-up
occurs and can be very significant. When stress build-up is relieved it will occur in the weakest
portion of the structural member or its connection to other parts of the structure. The stress may
result in tension cracks, shear cracks, and buckling.
e) Early thermal cracking of freshly placed concrete

Freshly placed concrete undergoes a temperature rise from the heat generated by the cement
hydration. The heat rise occurs over the first few hours or days after casting, then cools to the
surrounding ambient temperature. When cooling takes place two or three days after casting, the
concrete has very little tensile strength. Weak tensile strength, coupled with a thermally
contracting member, provide for the likelihood of tension cracks. Factors affecting early
temperature rise include:
Initial temperature of materials: Warm materials lead to warm concrete. Aggregate
temperature is the most critical.
Ambient Temperature: Higher ambient temperature lead to higher packs.
Dimensions: Larger sections generate more heat.
Curing: Water curing dissipates the build-up of heat. Thermal shocking should be
avoided.
Formwork removal: Early removal of formwork reduces peak temperature.
Type of formwork: Wood forms produce higher temperatures then steel forms.
Cement content: More cement in the mix means more heat.
Cement type: Type III cement produces more heat than most other cements used.
Cement replacements: Fly ash reduces the amount of heat build-up.
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f) Thermal Movements in Existing Cracks

Thermal stresses can be relieved in ways other than by the formation of cracks. Cracks that
are formed via other mechanisms, such as dry shrinkage cracking, may provide a location in
the member where thermal change strain can be absorbed. The crack moves with the same
cycle in the concrete member. Thermal movement taken up by these cracks reduces the
movement at planned expansion joints.
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Sulphate attack
Sulphate attack occurs as a result of the ingress of dissolved sulphate ions into concrete, which
subsequently undergo reactions with the hardened cement. Depending on the exposure
conditions, a number of different reactions are possible, whose impact on concrete properties
results either from expansion and cracking or loss in strength and integrity. These different
effects will be examined subsequently. However, it is first useful to examine where sulphates
arise in the environment.
Sulphate in the Environment
Sulphates can arise from two main sources in the environment seawater and soil and
groundwater. These sources are discussed below.
1) Sea water
Seawater contains relatively large concentrations of sulphate ions between 2500 and 3000
milligrammes per litre (mg/L), depending on the salinity of the water. The anion is associated
with sodium and magnesium cations and, to a lesser extent, potassium and calcium ions. Using
typical proportions of association, MgSO4 can be estimated to be present at concentrations
between 2400 and 2900 mg/L, with Na2SO4 present at concentrations between 4800 and 5800
mg/L. The high concentrations of magnesium sulphate mean that seawater can potentially be a
relatively aggressive sulphate environment.
2) Soil and Ground water
The extent to which sulphate in soil is available for ingress into concrete depends on the
solubility of the minerals present, as well as the extent to which groundwater is present and its
mobility. Soil can potentially contain a number of sulphate minerals, although some of these are
of low solubility. Common sulphate minerals are shown in Table, which shows that the most
soluble are sodium and magnesium sulphates. Sulphide minerals such as pyrite, marcasite and
pyrrhotite may also be present. Most of these sulphide minerals are of very low solubility. In
undisturbed soils rich in sulphide minerals, sulphate will only be present in significant quantities
in the first few metres of soil that has undergone long-term weathering processes that have led to
the gradual oxidation of sulphides.
Moreover, the first metre of soil will typically contain relatively low levels of sulphate
resulting from leaching to lower levels by infiltrating rainwater.
Disruption of soil during construction can potentially bring sulphide minerals in contact with air,
which allows the minerals to be oxidised to sulphate minerals at a relatively high rate. In highpH conditions, such as those produced in close proximity to hydrated Portland cement, this
process can be accelerated. Sulphur-oxidising bacteria, which may be present in soil, are also
capable of converting sulphide minerals into sulphates. In both cases, sulphide is oxidised to
sulphuric acid, which proceeds to react with other cations in the soil to form sulphate
compounds.
Peaty soils are also rich in sulphur, although much of this is present as organic
compounds rather than as inorganic minerals. However, this too can be oxidised to sulphate as a
result of soil disruption.
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Human activities may also introduce sulphur onto sites. Previous industrial operations
particularly those involving the handling and processing of fossil fuels may contaminate soil
with sulphates and sulphides. Activities of this type include coal mining, gas and coke processing
plants and iron and steel manufacture. Additionally, activities such as fertilizer manufacture and
metal finishing may also introduce sulphates onto a site.
In some cases, sulphate-bearing by-products from industrial activities may be introduced
onto sites as granular fill. These include blast-furnace slag, colliery spoil, furnace bottom ash
from coal-fired power generation and incinerator bottom ash from the combustion of municipal
waste. Demolition rubble can also potentially contain reasonably large quantities of soluble
sulphate.
Sulphate attack
The presence of soluble sulphates (Principally those of sodium, calcium and magnesium) is
common in areas of mining operations, chemical and paper milling industries. Sodium and
calcium are most common sulphates in soils, water and industrial processes. Magnesium
sulphates are less common, but more destructive. Soils or waters containing these sulphates are
often called alkali soils or waters.
All sulphates are potentially harmful to concrete. They react chemically with cement
pastes hydrated lime and hydrated calcium aluminates. As a result of this reaction, solid
products entering the reaction are formed.
The formation of gypsum and ettringite expands, pressurizes and disrupts the paste. As a
result, surface scaling and disintegration set in, followed by mass deterioration.
Mechanism
The most commonly encountered form of sulphate attack occurs in parallel with the
formation of ettringite (3CaOAl2O3 (CaSO4)332H2O) as a reaction product.
This type of attack occurs when the cations associated with the sulphate ions are sodium,
potassium or calcium. Ettringite is a reaction product of Portland cement hydration and plays
an important role during the early setting and hardening of cement.
However, when formed within relatively mature concrete in large enough quantities, the
effect can be problematic.
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For ettringite to be formed by sulphate ions entering hardened concrete, the sulphate needs to
come into contact with a source of aluminum and calcium.
In a mature cement paste, aluminum is present as ettringite, Al2O3Fe2O3mono (AFm)
hydration products or is substituted within the calcium silicate hydrate (CSH) gel.
Aluminum from AFm phases is usually more soluble than that from CSH gel, and so it is
normally these phases that are involved in ettringite formation.
Normally, the AFm phase present will be monosulphate (3CaOAl2O3CaSO412H2O),
although mix constituents and environmental conditions may produce AFm phases including
Friedels salt (3CaOAl2O3CaCl210H2O),
Monocarbonate (3CaOAl2O3CaCO311H2O) and
Hemicarbonate (3CaOAl2O31/2CaCO31/2CaO.12H2O).
The reaction with monosulphate is as follows:
The additional calcium required for this reaction is obtained from different sources,
depending on the cation associated with sulphate.
Where sulphate is present as CaSO4, the associated ion provides all of the calcium required
for the reaction.
However, where sodium or potassium sulphate is involved, calcium comes either from the
hydration products portlandite (Ca (OH) 2) or CSH gel.
Where calcium is obtained from CSH gel, the Ca/Si ratio of the gel declines, and the gel is
said to have become decalcified. When no further AFm phases remain, the sulphate ions
combine with calcium ions to form gypsum (CaSO42H2O).
It is often stated that the expansion of concrete undergoing this type of sulphate attack is the
result of the solid volume of ettringite being significantly greater than that of solid reactants.
However, this is true of other cement hydration products, yet their precipitation has little
impact on paste volume.
It has been proposed that the expansion is the result of the decalcification of CSH gel, which
leads to greater swelling of the gel as a result of water imbibitions.
Regardless of whether this is the case; decalcification will lead to loss in strength.
Methods of controlling sulphate attack
Sulphate resistance of concrete can be improved by reduction in water cement ratio and
an adequate cement factor, with a low tricalcium aluminate and with proper air entrainment.
With proper proportioning, silica fume, fly ash and GGBS generally improve the resistance of
concrete to sulphate attack, primarily by reducing the amount of reactive elements (such as
calcium) needed for expansive sulphate reactions. Generally the methods for controlling sulphate
attack are
a) Use of sulphate resisting cement
b) Quality concrete
c) Use of air-entrainment
d) Use of pozzolana
e) High pressure steam curing
f) Use of high alumina cement
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a) Use of sulphate resisting cement

The most efficient method of resisting the sulphate attack is to use cement with low C3A content.
In general, it has been found that a C3A content of 7% gives a rough division between cements of
good and poor performance in sulphate waters.
b) Quality concrete
As 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.
c) Use of air-entrainment
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.
d) 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 insoluble nonleachable 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.
e) 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 a high
pressure steam curing method is adopted.
f) 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 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 interior it. It should be remembered that high alumina cement may not be
show higher resistance to sulphate attack at higher temperature.
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Durability of Concrete

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Durability of Concrete

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Durability of Concrete

Topics discussed are

Figure 1 Definition of Service Life

8) As with most durability characteristics, adequate curing of concrete is of great

Frost action (Freezing and thawing attack)

Freeze Thaw Disintegration

Strength loss in the cement matrix

Improving the Fire Resistance of Concrete

Thermal Properties of Concrete

The range of diffusivity of concrete is between 0.002 to 0.006 m2/h

b) Uneven Thermal Loads

d) Restraint volume changes

e) Early thermal cracking of freshly placed concrete

f) Thermal Movements in Existing Cracks

a) Use of sulphate resisting cement

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