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Understanding Cement
Understanding Cement
C) may not
accurately reflect strengths in large pours of concrete where the heat of
hydration has raised the temperature of the concrete.
Using mineral additions may make the concrete more susceptible to carbonation
(Chapter 9.3) because depletion of calcium hydroxide from the cement paste to
produce additional C-S-H lowers the alkalinity of the pore fluid. To some extent,
this susceptibility is offset by the lower permeability to CO2 of concretes
containing mineral additions.
7.2 Blastfurnace slag
7.2.1 Blastfurnace slag composition
Slag used in concrete is a by-product of iron smelting. Limestone is added as a
flux during smelting to combine with silica and other impurities in the iron ore. If
the resulting liquid is tapped off and cooled rapidly, it produces a latently-
hydraulic glass. If the liquid is cooled slowly, an unreactive crystalline material is
produced, known as air-cooled slag, and is used as an aggregate.
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Slag used in concrete is largely composed of a calcium aluminosilicate glass,
often with some crystalline phases, particularly gehlenite (C2AS) and merwinite
(CMS2). The crystalline fraction is unreactive.
When allowed to cool slowly the crystalline content of the slag increases, with a
consequent decrease in hydraulicity. Rapid cooling is generally achieved by one
of two methods:
# Granulated blastfurnace slag is produced by pouring liquid slag into a high
volume of water (Figure 7.1); the water may be running through a trough,
or it may be a still pond. The resulting cooled slag generally contains
90%-98% glass.
# Pelletised slag is produced by pouring the liquid slag onto a rotating drum
cooled by water (Figure 7.2). The slag breaks into pellets and is propelled
through the air in a chamber full of water spray. Pelletised slag used in
concrete generally has a lower glass content than granulated slag,
typically 70%-90%.
A small amount (~5%) of crystalline material in slag may be beneficial; increases
in the crystalline content of the slag up to a total of about one-third may result in
only a slight loss of concrete strength (4).
Chemical moduli have been used to evaluate slags. For example, British Standard
BS EN 15167-1: 2006 specifies that (CaO+MgO)/(SiO2)>=1 and that
CaO+MgO+SiO2 must be at least
2
/3 the total mass. An earlier version, BS6699:
1986 used the modulus (CaO+MgO+Al2O3)/(SiO2) >=1.
Figure 7.1 Production of granulated blastfurnace slag: left - a fast-moving stream of
water; right - molten slag flows into the water stream and is quenched (courtesy Hanson
Cement).
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Figure 7.2 Principle of production of pelletised slag (courtesy Hanson Cement).
Figure 7.3 Granulated blastfurnace slag,
before grinding.
Figure 7.4 SEM image of granulated
blastfurnace slag (gbs) after grinding.
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Slag is an impure calcium aluminosilicate glass (Table 7.1).
Table 7.1 Chemical composition of a typical blastfurnace slag used in concrete in the UK,
(source: Hanson Cement, UK).
SiO2 Al2O3 FeO CaO MgO K2O Na2O S
2-
LOI Total
36.0 13.0 0.5 40.0 8.0 0.5 0.3 0.8 0.5 99.6
Balance is due to minor oxides, typically P2O5, MnO, TiO2, and possibly a trace of SO3.
Because of the need for precise control of the iron production process, the slag
from a given source tends to have a consistent composition. As used in cement,
the material is essentially a crushed glass and so the composition varies little
between individual particles.
Whether a slag is suitable for use as a cementitious material in a composite
cement depends mainly on how reactive the material is. Reactivity will depend
particularly on the composition of the glassy fraction, total glass content and the
particle size to which the material is ground, but the relationships are not
straightforward.
For example, a fast-cooled slag with a high glass content will have the same bulk
composition as a slag from the same liquid that was cooled more slowly.
However, the composition of the glassy fraction will be different because the
composition of the liquid will have changed during cooling as crystals formed
from the melt. The glassy fractions of the two slags cooled at different rates may
therefore have different reactivities.
7.2.2 Blastfurnace slag as a cementitious material
When used as a mineral addition, slag typically comprises 20%-70% of the total
cementitious material, although higher levels are used for specific applications.
The main technical benefits of using slag in a composite cement are:
# Will give higher later strengths, but generally lower early strengths.
# Reduced concrete permeability.
# Improved durability (sulfate resistance; reduced likelihood of alkali-silica
reaction; reduced chloride penetration).
# Lower heat of hydration reduces risk of thermally-induced cracking.
# Lighter colour of concrete.
In addition, the general benefits of using composite cements discussed in
Chapter 7.1 apply to the use of slag, especially the following:
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# Using slag reduces the rate of depletion of raw materials used to produce
Portland cement.
# Using slag reduces the energy required for production of cementitious
materials per unit volume of concrete.
# Using slag reduces the total carbon dioxide emissions per unit volume of
concrete.
Lets look at these in a little more detail:
Strengths
Partial replacement of Portland cement by slag generally results in lower early
strengths, due to the slower rate of reaction of the slag. Later strengths should
be higher in a suitably-designed mix. In mature concrete, more residual
unhydrated slag is likely to persist than unhydrated Portland cement in an
equivalent mix. After a year, perhaps 50%-75% may have reacted, but the actual
figure will be dependent on factors including the w/s ratio, the intrinsic reactivity
of the slag, the proportion of slag in the mix and the fineness of the slag. Higher
later strengths, in a properly designed and executed mix, are mainly due to
enhanced C-S-H formation.
Permeability and durability
Mature concrete made with cement containing slag is generally of lower
permeability to water than concrete made with Portland cement only; this should
give improved durability. Chloride and sulfate penetration should be lower, so
chloride-induced steel corrosion or sulfate attack are less likely in a well-designed
and implemented concrete mix. Alkali silica reaction (ASR) is also less likely,
partly because partial replacement of PC by slag reduces the total available alkali
but also because slag hydration lowers the calcium hydroxide content and the
alkalinity of the cement pore fluid.
Heat of hydration
Compared with Portland cement, slag typically hydrates more slowly as it is a
less-reactive material. The heat of hydration of a composite cement containing
slag is therefore less than that of a comparable PC-only mix. Both the rate of
heat evolution and the total heat evolved are lower in mixes where Portland
cement is partially replaced with slag.
Colour
The grey colour of Portland cement is due to the ferrite phase. Slag does not
normally contain ferrite or other strongly-coloured minerals so partial
replacement of Portland cement with slag should result in a lighter colour of
concrete. Although slag powder is almost colourless, fresh fracture surfaces of
concrete containing slag are usually a blue-green colour. This is thought to be
due to sulfide from the slag entering the hydration products, probably the AFm
phase. After a few days, the blue-green colour fades as the sulfide oxidises.
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7.2.3 Hydration products in mixes containing slag
The hydration products in a composite cement containing Portland cement and
slag are similar to those of Portland cement. There is likely to be more C-S-H and
less CH, and the C-S-H will have a higher Si/Ca ratio. Because of the additional
available alumina from slag hydration, most sulfate is likely to be contained in
AFm phase and there may be little or no ettringite, unless fine limestone is also
present (Chapters 6.3 and 12.2).
Hydrotalcite (see Chapter 6.3): ([Mg0.75 Al 0.25 OH)2](CO3)0.125(H2O)0.5
is likely to be present in small quantities; it may also occur in small amounts in
an ordinary Portland cement mix if the MgO content of the cement is high. Its
effect on strength will probably be negligible, but it will slightly alter the balance
between available sulfate and alumina and so could affect the relative proportions
of AFm phases (eg; monosulfate: hydroxy-AFm: monocarbonate) and ettringite.
7.3 Low-lime fly ash
Fly ash (pulverised fuel ash, or pfa) is produced by power stations burning
pulverised coal and is the non-combustible mineral residue separated from the
flue gas. The composition of the ash will evidently depend on the minerals
present in the coal.
7.3.1 Fly ash composition
Low-lime fly ash used in Europe typically contains high proportions of silica and
alumina (Table 7.2) and contains a high proportion of glass. This broadly
corresponds to a Class F ash in the USA.
Table 7.2 Chemical composition of a low-lime fly ash used in concrete (UK-sourced
ash).
SiO2 Al2O3 Fe2O3 CaO MgO K2O Na2O SO3 Total
53.0 26.6 8.0 2.2 1.2 4.2 1.6 1.0 97.8
Balance is mainly carbon, with minor oxides including P2O5 and Mn2O3.
The glass content of fly ash is typically 70%-90%, with the bulk of the crystalline
material consisting of quartz (SiO2) and mullite (an aluminium silicate, Al6Si2O13
or Al6Si3O15)
The bulk of most fly ash is composed of spherical particles, ranging in size from
under 1!m to about 50!m, although some particles may be up to 100!m in
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diameter. Most particles are solid (with some air bubbles) although some are
hollow shells.
Figure 7.5 Coal fired power station, source
of fly ash used in concrete. (Photo courtesy
UK Quality Ash Association.)
Figure 7.6 SEM image of fly ash particles,
as used in concrete.
Most fly ash particles are mainly composed of an impure glassy aluminosilicate.
However, because they are formed individually from mineral assemblages in coal,
the composition of each particle is slightly different, or sometimes very different.
While most of the aluminosilicate particles are of broadly similar composition,
some particles are iron-rich or silica-rich and some oddities are rich in other
oxides eg: titanium dioxide.
Some fly ash is calcareous; these ashes are typically higher in CaO, SO3 and MgO
and contain less SiO2 and Al2O3 compared with siliceous fly ash. These ashes are
described as Class C fly ash in the USA if the sum of the SiO2 and Al2O3 contents
is less than 70%. The following focuses on siliceous fly ash.
7.3.2 Fly ash as a cementitious material
When used as a mineral addition, fly ash typically comprises up to 30% of the
total cementitious material, sometimes more. The main technical benefits of
using fly ash in a composite cement are:
# Can give higher later strengths in large pours of concrete; ultimate
strengths in small pours or mixes cured at ambient temperature will be
similar to, or lower than, those of Portland cement mixes for the same
total cementitious content.
# Because fly ash particles are spherical, mixes containing fly ash require
less water for the same workability compared with a mix containing
Portland cement only; this reduces permeability.
# The intrinsic paste permeability is reduced, probably due to an increase in
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the Si/Ca ratio of the C-S-H, (Chapter 7.1).
# Improved durability (sulfate resistance; reduced likelihood of alkali-silica
reaction; reduced chloride penetration).
# Lower heat of hydration reduces risk of thermally-induced cracking.
# Less efflorescence.
# Less shrinkage and creep.
In addition, the general benefits of using composite cements outlined in Chapter
7.1.2 apply to the use of fly ash.
The main properties determining whether an ash is suitable for use in concrete
are its pozzolanic reactivity and the ability of the ash to reduce the concrete
water demand. Too much carbon in the ash increases the water demand, affects
the colour of the concrete and can affect the action of concrete admixtures.
Carbon in ash can usually be accommodated in the mix design, provided the
carbon content does not change; a variable carbon content is more difficult to
deal with.
Strengths
Concrete in which fly ash has replaced some of the Portland cement would be
expected to have lower early strengths due to the slower rate of reaction of the
ash particles compared with Portland cement. However, the basis of any
comparisons has to be considered carefully as one of the principle benefits of the
use of fly ash is that the w/s ratio can be lowered for the same workability, due
to the particle shape of the ash. Other adjustments to the mix design may also
be made.
For the same total cementitious contents cured at ambient temperature, a
concrete containing Portland cement and fly ash would be expected to show both
lower early strengths and lower 28-day strengths compared with a Control mix
containing just Portland cement. At later ages, the strength growth curve for the
Control mix would flatten off but the fly ash mix would continue to gain strength
and may overtake after three months to a year.
In large pours of concrete where the heat of hydration raises the concrete
temperature appreciably, the mix containing fly ash will still be weaker than the
Portland cement Control mix at early ages, but will tend to overtake the Control
later; the larger the pour and higher the temperature, the sooner the fly ash
concrete is likely to become the stronger of the two mixes. (Note that the curing
temperatures will not be the same; for equivalent pours, the mix containing fly
ash will have a lower heat of hydration, see below).
Cement and fly ash finenesses will affect the rates of strength growth in these
comparisons.
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Permeability and durability
The benefits of using fly ash in a composite cement in relation to permeability
and durability are broadly similar to those of using slag (Chapter 7.2.2).
Heat
Low-lime fly ash reacts more slowly than ordinary Portland cement and
consequently it is widely used in large concrete pours, such as dams, where high
fly ash contents are often used. The maximum temperature reached by the
concrete is much reduced, lessening the chances of thermal fracturing and
increasing the final concrete strength.
Other benefits
Benefits cited by the ash industry, in addition to the above, include a reduction in
efflorescence and in shrinkage and creep. Efflorescence is caused by soluble salts
reaching the surface (particularly calcium hydroxide); these salts are usually
derived from the cement. If the cement content of a concrete is reduced by
partial replacement of Portland cement with fly ash, it follows that less soluble
material will be in the mix and so the likelihood of efflorescence occurring will be
lessened. Additionally, if fly ash reduces the permeability of the paste, less
soluble material will reach the surface, again reducing efflorescence.
The magnitude of any drying shrinkage and creep in concrete is related to the
w/c or w/s ratio of the mix. Since using fly ash as a mineral addition in cement
enables the use of a mix of lower w/s ratio for the same workability, shrinkage
and creep should be reduced.
7.3.3 Hydration products in mixes containing fly ash
Silica released from fly ash hydration forms C-S-H, the necessary lime being
derived from CH from cement hydration and by increasing the Si/Ca ratio of the
C-S-H.
Alumina is also released; some enters the C-S-H structure, increasing the Al/Ca
ratio of the C-S-H. The remaining alumina forms other compounds, including AFm
phase, hydrogarnet (mainly C3AH6) and stratlingite (C2ASH8).
Typically, between a quarter and a half of the ash may eventually react (this
might take months or years), depending on factors including ash glass content,
hydration temperature, percentage of cement replacement and the alkali content
of the Portland cement. It is primarily the glassy phase that reacts; the
crystalline inclusions, mainly quartz and mullite, are generally inert. Mullite and
quartz crystals can occasionally be seen in SEM images of fracture surfaces,
protruding from part-reacted ash particles where glass has been extracted by
reaction with the cement pore fluid.
While fly ash contributes to later strength gain through the pozzolanic reaction,
the slow rate of reaction means that, initially, fly ash is almost chemically inert in
the early stages of Portland cement hydration. Before any significant fly ash
reaction has occurred, as with fine limestone particles, the ash particles provide
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nucleation sites on which hydration products can form from solution, increasing
the rate of Portland cement hydration at early ages. This partly offsets the slower
rate of strength growth due to the lower fly ash reactivity compared with the
Portland cement it has replaced.
The pozzolanic reaction process by which fly ash contributes to concrete strength,
is believed to be that sodium and potassium in the pore fluid reacts with silicate
material extracted from the fly ash by the action of hydroxyl ions. An alkali-
silicate gel is formed, which is unstable in the presence of calcium and is rapidly
converted to C-S-H.
The presence of sodium and potassium hydroxide in the cement pore fluid will
increase the pore fluid alkalinity and accelerate fly ash reaction. However, lime
(calcium hydroxide) does not contain sodium or potassium hydroxide although a
lime/fly ash mix produces an hydraulic binder. This shows that sodium and
potassium hydroxide are not essential to fly ash reaction; the alkalinity produced
by the lime is sufficient, although the reaction rate will be slower.
Figure 7.7 Polished section of concrete
made using Portland cement (70%) and fly
ash (30%). Key: c-(and other similar bright
features) are relicts of partly-hydrated
cement particles; s-silica sand; arrowed
features are examples of fly ash particles,
but there are many more. Note that the fly
ash particles are not all the same grey
level; this is because each particle has a
different composition, usually only slightly.
Most are medium-grey and composed of
aluminosilicates; a few are bright, iron-rich,
particles. (NB: in backscattered electron
images, grey level is approximately
proportional to mean atomic number:
Fe2O3, for example, will appear brighter
than SiO2.).
Figure 7.8 Polished section of concrete
made using Portland cement (30%) and
slag (70%). Key: circled features are relicts
of partly-hydrated cement particles; s-sand
particles, mainly silica and feldspar;
arrowed, light grey particles are slag
particles. A dark reaction rim can just be
seen around some of the slag particles. In
contrast with the fly ash particles in Figure
7.7, all the slag particles here are of the
same grey level, as they are all of similar
composition having been quenched from
the same liquid.
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7.4 Microsilica (silica fume)
Microsilica is a by-product of silicon production. It is composed largely of
structurally-amorphous silicon dioxide spheres, typically 0.1 !m across. It is a
highly pozzolanic material, white, grey or almost black in colour and has a high
pozzolanic activity, more so than fly ash.
Because it has a high surface area, it has a high water demand and this limits the
level of cement replacement by microsilica unless water-reducing admixtures are
used.
As it is composed largely of silica, the main chemical effect of microsilica is to
increase the C-S-H content of the paste by reaction with CH from Portland
cement hydration. Unlike fly ash or slag, where a significant proportion of the
material remains unreacted, microsilica will usually react largely or fully. The
increased proportion of C-S-H should reduce the overall porosity of the concrete
and increase the strength; also, the increased Si/Ca ratio of the C-S-H, as
discussed above (Chapter 7.1) may reduce the interconnectivity of the pores.
The main benefits of using microsilica are:
# An increase in strength; microsilica is often used in high-strength
concrete.
# The high surface area of microsilica reduces bleeding at the concrete
surface.
# A decrease in permeability to water (by a factor of 10-100 compared with
a Portland cement-only mix) and hence improved durability and resistance
to chloride or sulfate ingress.
# A reduction in the likelihood of ASR due to the decreased pH as a result of
consumption of CH to form C-S-H; the lower permeability to water should
also be beneficial in this regard.
Microsilica is available in several forms: densified, undensified and as a slurry;
each type is best suited for particular applications. It is important to disperse
microsilica adequately, since undispersed clumps will behave essentially as larger
particles of reactive silica, producing alkali-silica gel.
For more information on microsilica in concrete, see Lea (5) or Taylor (6).
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7.5 Limestone
Limestone is a mineral addition widely used in cement. It is neither pozzolanic
nor latently hydraulic.
Small additions of limestone (up to 5%) have been considered in Chapter 5.8. In
the context of mineral additions, the proportions of limestone in the cement are
much higher. For example, European Standard EN 197-1 specifies cements
containing 6%-20% limestone (CEM II/A-LL)
1
and 21%-35% limestone
(CEM II/B-LL).
Generically, such cements are referred to as Portland-limestone Cement (PLC).
PLC has been used in Europe for many years and is now becoming more widely
used elsewhere. To take an example of how PLC is used, in the UK it is widely
used in both precast and ready-mixed concrete; in Europe as a whole, PLC
represents about a quarter of the cement market.
The main benefits of PLC are:
# Cost
# Shrinkage control
# Reduction in bleeding
# Reduced CO2 emissions
PLC may be produced by intergrinding limestone with clinker, or by blending
limestone powder in the mixer. (These alternative methods are likely to produce
different clinker and limestone particle sizes with possible effects on cement
characteristics). Limestone interground with clinker grinds preferentially, as it is
softer than clinker; PLC therefore is usually ground finer than Portland cement to
ensure the clinker particles are sufficiently fine.
Fine limestone in cement is often regarded just as a filler and indeed it does fill
gaps between clinker particles. However, as already discussed (Chapter 6.3),
limestone is not inert, as some of it takes part in the hydration process.
The dilution effect of replacing some of the clinker with limestone can be offset
by grinding the clinker more finely. For the same water/cement ratio, PLC
concrete may have a lower 28-day strength than a concrete containing Portland
cement only, and a higher cement content may be needed to produce similar
strengths.
For the same concrete strength, PLC has similar durability characteristics to
Portland cement in most respects, although its resistance to sulfate attack is still
being evaluated, particularly with regard to thaumasite formation. (Sulfate attack
and thaumasite are discussed in Chapter 9).
1
Or CEM II/A-L; CEM II/B-L for lower purity limestone, see Chapter 10.
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In PLC concrete, the rate of hydration of alite is increased by the presence of fine
limestone, giving good early strengths. Hemicarbonate and monocarbonate are
formed from the reaction of aluminate phase with some of the limestone; most of
the sulfate in the cement is likely to be present as ettringite. Only a small
proportion of the limestone will react, although the proportion will increase in
concrete containing Portland cement with a higher aluminate content, or if
additional alumina is available from slag or fly ash in the mix.
Monocarbonate and hemicarbonate formation fill pore space within the concrete,
reducing permeability and thereby increasing durability. They may also make
some contribution to strength.
The increased use of PLC is highly likely if the proportion of Portland cement in
concrete is to be reduced for environmental reasons. Limestone is readily
available, but other mineral additions (particularly slag and fly ash) are in limited
supply. Also, it is undesirable to transport bulk materials further than necessary.
The availability of fly ash and slag depends on coal-fired power generation or iron
smelting; they are not available everywhere without being transported over long
distances but limestone is readily available wherever cement is produced.
Herfort describes the hydration and performance of PLCs (7).
References, Chapter 7
1. Cement Chemistry, H F W Taylor, Thomas Telford, 2nd ed. 1997, pp291-
293.
2. Source: http://www.ukqaa.org.uk/Datasheets_PDF/Datasheet_8-
3_Feb_2009.pdf
3. Source: http://www.ukqaa.org.uk/Datasheets_PDF/Datasheet_8-4_Feb
2009.pdf
4. Demoulian et al, 7th International Congress on the Chemistry of Cement,
Vol 2, 1980.
5. Lea, particularly Chapter 12; also other references in Lea check Lea
index
6. Cement Chemistry, H F W Taylor, Thomas Telford, 2nd ed. 1997, p284.
7. Portland Limestone Cements, D Herfort, The First International
Conference on New Cements and their Effect on Concrete Performance"
HBRC-Helwan University, Cairo, 16-18 December 2008. Currently in press
in the HBRC journal. http://www.hbrc.edu.eg/journal/Default.aspx
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Additionally:
Some excellent datasheets (downloadable pdf files) on the use of fly ash in
concrete are available from the UK Quality Ash Association web site at:
http://www.ukqaa.org.uk/Publications.html#TechnicalDatasheets
Similarly, equally-excellent datasheets on the use of slag in concrete in addition
to Reference 1 above are available from the Hanson UK web site at:
http://www.heidelbergcement.com/uk/en/hanson/products/cements/ggbs_and_r
elated_products/ggbs_.htm
There is more on slag at the UK cementitious slag makers association web site:
http://www.ukcsma.co.uk/index.html
(Web sites have an irritating habit of changing, so if these pages change and the
links do not work, look around the web site as the pdf files will probably still be
available somewhere.)
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8 Cement variability
Here, we use cement variability to mean the extent to which cement from the
same source, and produced to the same specification, varies over time. In other
words, if you buy a bag of cement produced from clinker made on Monday and
then another bag from clinker made on Friday, will the cement in the two bags
behave in exactly the same way when mixed with water?
On a larger scale, if you receive a delivery of bulk cement to a silo today, will the
cement in this delivery behave identically to that delivered last week or last
month?
The short answer is: Yes, probably. For most practical purposes, they should all
behave in such a similar way that it wont be easy to distinguish cement from the
two bags or deliveries. However, you might just possibly notice differences in
cement characteristics. These differences may be so slight as to make no
practical difference but occasionally they may cause problems.
The main differences that may be noticed typically relate to colour, setting times,
early strengths, later strengths or how the cement responds to admixtures. If
you are manufacturing pre-cast concrete products, early strengths are likely to
be important as they will control how quickly you can de-mould the product and
re-use the mould. If you are an engineer requiring a minimum 28-day strength,
then later strengths will probably be your prime concern.
8.1 In defence of the cement producer
The cement producer may sometimes be forgiven for feeling unloved. He (or she)
is blamed for the perceived high price of his product and, when anything goes
wrong, everyone immediately blames the cement.
Most cement producers normally go to great lengths to ensure a consistent
product. However, achieving this is this is not always easy.
A typical modern cement plant may produce 2000-3000, or more, tonnes of
cement every day. The raw materials from the quarry will inevitably be of
variable composition, fuels will vary in their ash content, ash composition and
calorific value. These days, in efforts to reduce fossil fuel use, alternative fuels
Cement variability
used to make cement may include waste paper, car tyres or solvents in addition
to the normal gas, oil or coal. The availability and composition of each of these
may vary on a daily basis, requiring constant adjustments to the raw meal
composition and fuel mix. Given all this variability, it would be surprising if the
behaviour of the product never fluctuated just a little.
Despite all of the above problems, in most places modern cement is more
consistent and of a higher quality than ever before. Improvements have been
made possible through developments in the major components of the cement
plant - the kiln and the raw materials and cement mills - but especially in
computer-controlled operations and in on-line analysis.
Prior to a few decades ago, analyses of everything - raw materials, blended raw
materials, clinker and cement - would have been carried out by taking samples,
dissolving them in suitable reagents, then quantifying compositions by titration or
gravimetrically, followed by calculation using pencil and paper. This might all take
several hours, or even up to 24 hours. Today, online sampling and analysis is
carried out automatically in minutes using X-ray fluorescence and X-ray
diffraction.
If, for example, the raw feed composition starts to drift from the target values,
the change should be noticed quickly and corrective action taken, again probably
automatically. Such early recognition of deviations from target compositions,
followed by rapid corrective action, should minimise variability in the composition
of the cement.
Tests carried out on the cement by the manufacturer will depend on the standard
to which the cement is produced, but will typically include tests on composition,
tests for expansion on hydration and tests on strength in standard mixes. These
tests should ensure that the cement conforms to the appropriate standard.
It is simply not possible for a cement producer to test his cement with all of the
materials with which it may be used. These could include fly ash, slag, microsilica
and any of hundreds of admixtures. Even a few basic permutations of all of these
would produce thousands of mixes to be tested - not just once, but every day, or
hour or whatever analysis interval was deemed appropriate. This would clearly be
unrealistic and anyway would add greatly to the cost of the cement.
The price of cement is often a key factor in making purchasing decisions. A major
cement user will often contract with a particular supplier for a period of time (eg:
a year) and a pound or dollar or two either way in the cost per tonne may make
all the difference in deals worth millions. Adding an expensive battery of tests
that will be largely unnecessary wont appeal to either the cement producer or
purchaser.
The cement makers lot is not, then, always a happy one. He has to contend with
variable raw materials and variable fuels. Increasingly, he also has to comply with
environmental legislation that requires him to reduce CO2 emissions or pay heavy
penalties; in turn this may involve the use of alternative fuels that may
themselves have the potential to cause more variability in the product.
He has to comply with other environmental laws limiting what can be emitted
from his site. In more densely-populated areas he has the general public living
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Cement variability
nearby, for whom the cement producer is invariably responsible for dust from any
source falling onto their house or car. He has customers for whom price often
appears to be a more important factor than the supply of a consistent product or
good customer service - at least until something goes wrong.
On top of all that, he has shareholders looking for a return on the tens or
hundreds of millions that they invested to build the cement plant in the first
place. If he fails to deliver, the shareholders will sell him to another cement
producer who will demolish his kiln and turn his quarry into a shopping mall. Its
enough to make anyone wish they had listened to mum and dad and become a
...lawyer or a doctor or a civil engineer.
8.2 Causes of cement variability
Lets restore some objectivity. If it is unrealistic to expect cement from a given
source never to vary, what degree of variation might be expected and what might
be the cause(s)?
Obviously, the purchaser can expect that all cement will conform to the standard
to which it was produced. However, the standard is likely to permit a range of
physical and compositional characteristics. Usually, a purchaser has the choice of
several different sources of cement, all nominally similar and produced to the
same standard, and he will probably have a preferred source. This preference
may be based on price or on technical considerations.
Perhaps one source has a particularly dark or light colour that suits the
application better than other cements, or maybe it has a particularly good early
strength, or it just works better in his process than other alternatives.
Suppose you are a producer of concrete products who has been using cement
from a particular source for some months without any problems; suddenly, you
notice a change in the strength of the concrete, or that the cement has a
different colour. What may have happened?
Firstly, it might be a different cement, or cement made from a blend of the usual
clinker with other imported clinker. This might happen, for example, when a
cement kiln is shut down for periodic maintenance or because of a technical
problem. The cement producer may bring clinker in from elsewhere to
supplement the lost production. Usually, he will advise his larger customers in
advance that this will happen, or he should do. If a change in cement
characteristics coincides with a kiln shutdown, this may well be the explanation.
With luck, normal cement characteristics will be restored when the kiln restarts.
However, suppose you notice changes in behaviour over time in cement from a
single source, even though no major alterations in the raw materials or clinker
composition were apparently made over this period. Surely something must have
changed? Well, yes it might have.
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Colour: changes in the colour of cement may be due to differences in the
amount of ferrite in the clinker; since ferrite is dark grey or black, it gives clinker
its characteristic grey or black colour. If the proportion of ferrite changes, the
colour may also change. A change in the ferrite content may be due to a change
in the overall oxide composition, but differences in burning conditions can also
affect colour.
Strength: changes in strength may be due to a number of causes; obviously,
lower strengths tend to be the cause of more concern than increased strengths. A
few of the most common causes of lower strengths include:
# Cement fineness: the cement particles may be coarser. This could be
due to a difference in the overall fineness of the cement, or to differences
in particle size distribution. This might be due to an intentional change in
cement fineness, or it might be due to a temporary mill problem. Note
that this is primarily a physical difference, rather than chemical. It is
clearly related to the performance or operation of the cement mill,
although other factors may have been the trigger. One example might be
that the raw feed to the kiln contains more coarse silica resulting in large
clusters of belite, hard and resistant to being ground, getting into the
cement. Another could be that the normal cement mill is under repair and
the alternative mill produces a different particle size distribution.
# Lower alite content: concrete strength is mainly due to calcium silicate
hydrate formation from the hydration of alite and belite. Alite is more
reactive than belite, so if less alite is present in the cement, early
strengths are likely to be lower. If there is less alite, there is likely to be
more belite (provided that the silica ratio of the clinker has not altered
appreciably); later strengths may be restored to near-normal as belite
hydration continues.
# Different kiln conditions: for good early concrete strength it is not
simply the total amount of alite present that is important, but the
reactivity of the individual alite crystals. The reactivity of the alite (and
belite) crystals is higher if the clinker is brought to burning temperature
rapidly; the temperature maintained for as long as is necessary and the
clinker cooled as rapidly as possible. The length and temperature of the
flame in the kiln is of prime importance in this. Other factors are also
relevant, for example, the size of the clinker nodules will affect the rate at
which the clinker cools-the interior of coarser nodules will cool more
slowly. Overburning or underburning the clinker can also cause strength
loss, as can reducing conditions in the kiln.
# Sulfates - fixed w/c ratio v fixed slump: sulfates affect setting
properties by controlling C3A hydration. As discussed in Chapter 6.3, if
there is insufficient sulfate in solution in the pore fluid, flash setting may
occur, with the rapid formation of AFm phase. Conversely, if there is
excess sulfate in solution (possibly caused by high mill temperatures),
false setting may occur due to the growth of gypsum crystals. Flash or
false setting are both extreme cases; it is more likely that a very small
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amount of either may occur, insufficient to cause a set but enough to
slightly stiffen the mix or alter the performance of an admixture.
Gypsum is often considered to be the main form of sulfate in cement. In
practice, as we've seen, cement is likely to contain more than one form of
sulfate. Some will be clinker sulfate and some will be added at the cement
mill as gypsum. Clinker sulfate may typically contain several different
sulfates (eg: calcium langbeinite, arcanite, aphthitalite) and the added
gypsum may contain gypsum and natural anhydrite. The gypsum may be
decomposed during milling to hemihydrate or anhydrite. The cement
might then contain up to five or six different forms of sulfate, all with
different solubilities. The objective is that sufficient sulfate should be in
solution to control C3A hydration, but not enough to cause the
precipitation of gypsum. This is a delicate balance.
Waste calcium sulfate is increasingly used; usually, this is gypsum in the
form of materials such as plasterboard and can sometimes have
deleterious effects.
Syngenite formation (CaSO4.K2SO4.H2O - calcium potassium sulfate
hydrate) can occur in cements with a high K2O content. This may cause
false set due to crystal growth. Since syngenite formation removes sulfate
from the pore fluid, flash set may then also occur.
Sulfate solubilities are affected by temperature. The different forms of
calcium sulfate have lower water solubilities as temperatures increase;
arcanite (potassium sulfate) behaves more conventionally, becoming more
soluble at higher temperatures. Whether incipient flash or false set occurs
may therefore depend on the temperature of the mix.
Provided that test concrete (or mortar) mixes are prepared at a constant
water-cement ratio, minor imbalances in the rate of supply or
consumption of sulfate should not make much difference to strengths.
Specifications for cement in national standards normally specify testing at
particular water-cement ratios. However, the ready-mixed concrete
industry, and others, generally prepares concrete to a particular slump,
not to a particular water-cement ratio.
Suppose in a concrete produced at a ready mix plant, the cement pore
fluid becomes slightly super-saturated with respect to gypsum; a small
amount of gypsum will precipitate and the mix will stiffen slightly. The
operators response will probably be to add more water to restore the
desired slump. The hardened concrete will then be weaker at all ages, due
to the additional water. We now have the interesting situation in which the
cement manufacturer correctly says that his tests show that his cement
produces mortar or concrete of normal strengths. Conversely, the
concrete producer equally correctly says that, using the same cement, his
concrete strengths are lower than normal. The problem is that the testing
procedures are not the same.
This situation could arise, for example, where two cements have a similar
oxide composition but one has been milled hotter than the other,
decomposing the gypsum to hemihydrate. As hemihydrate is more soluble
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than gypsum, a small amount of gypsum may form in an incipient false
set, even though the mix is still workable. At the ready mix plant, the
reduction in slump is noticed and more water is added to compensate.
Anything that affects the rate at which the C3A requires sulfate to control
setting, or the rate at which sulfate becomes available from all sources,
may have a similar effect. This could be a change in the total cement
sulfate content, a change in the proportion of clinker sulfate to total
sulfate, a change in cement fineness, a change in the C3A content of the
cement, a change in C3A reactivity or a change in the extent to which C3A
and ferrite crystals are intergrown in the clinker.
# Optimum gypsum: the gypsum content of the cement affects the rate of
strength development and the volume stability of the concrete.
Given all the things that could go wrong, of which the above is really just an
introduction, you might feel that maybe cement isnt quite so reliable after all.
However, the extent to which that impression is wrong is really a tribute to the
evolution of the manufacturing process over many years. Of course, things can
occasionally go badly wrong, but, fortunately, that is now unusual. Or, at least, it
should be.
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9 Deleterious processes in concrete
9.1 Reactions between cement paste and aggregate
Reactions between hydrated cement and aggregate in concrete, or alkali-
aggregate reaction, can be divided into two main types: alkali-silica reaction and
alkali-carbonate reaction.
In alkali-silica reaction, alkalis in the cement paste fraction of the concrete react
with with certain types of reactive silica to form an expansive gel.
In alkali-carbonate reaction, aggregate containing dolomite reacts with hydroxyl
ions in the paste to form calcium carbonate plus magnesium hydroxide and
carbonate ions. The products of the reaction occupy a greater volume than the
initial reactants and so an expansive force is exerted on the surrounding
concrete.
Well consider these processes in more detail below.
9.1.1 Alkali-silica reaction
Background
Alkali-silica reaction (ASR) can cause serious expansion and cracking in concrete,
resulting in major structural problems and sometimes necessitating demolition.
Although first recognised in the 1940s in the USA, it wasnt until the 1970s that
ASR really became the focus of attention of concrete science worldwide. It also
came to the attention of the media, who promptly dubbed it concrete cancer.
Extensive research was undertaken, which later led to better practise in the
production of concrete to minimise the risk of ASR in the future. Of course, it
wasnt purely scientific interest that had led to research funding suddenly being
available; rebuilding major structures damaged by ASR was becoming expensive.
The reaction
ASR is caused by a reaction between the hydroxyl ions in the alkaline cement
Deleterious processes in concrete
pore solution in the concrete and reactive forms of silica in the aggregate. These
reactive forms of silica are typically chert, quartzite, opal and strained quartz
crystals. Other materials, such as glass can also produce ASR. Pyrex glass and
calcined flint have been used as test reactive aggregates in experimental
concrete mixes. Ordinary glass (as in household jars and bottles) is also reactive.
Undispersed agglomerations of microsilica can also cause ASR.
Silicate anions are detached from the reactive aggregate by hydroxyl ions in the
cement pore fluid; sodium and potassium ions are the ions most readily-available
to balance the silicate anions and an alkali-silicate gel is formed. This can take up
(imbibe) water and is mobile. The gel is unstable in pore fluid containing
dissolved calcium, and calcium silicate hydrate (C-S-H) is produced. This releases
sodium and potassium from the gel into the pore fluid, increasing the pore fluid
hydroxyl ion concentration, with the potential for continued reaction.
Figure 9.1 Alkali-silica reaction in multi-
storey car park, UK. (Photo courtesy The
Concrete Society).
Figure 9.2 Alkali-silica reaction in
highways structure (Photo courtesy The
Concrete Society).
The alkali-silicate gel increases in volume by taking up water, and so exerts an
expansive pressure. If the reactive particle is impermeable to the pore fluid, gel
forms at the surface. Some types of silica (eg: chert and opal) are permeable to
alkali in pore fluid and gel can form inside the aggregate, often near the centre of
the particle. Where gel has formed inside an aggregate particle, the aggregate
particle usually cracks, with the crack extending into the surrounding concrete
(Figures 9.3-9.5).
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Deleterious processes in concrete
Figure 9.3 ASR in concrete viewed in thin-section;
alkali-silica gel (arrowed) almost fills the crack
extending from the chert particle at the right beyond
the left of the image. Yellow material is resin used in
specimen preparation.
Figure 9.4 SEM image of ASR in chert
particle (centre); internal microcracking is
widespread and some cracks extend into
the surrounding concrete.
Figure 9.5 Detail of Figure 9.4 showing gel
extruded from chert particle into a crack in
the concrete. Ettringite is also present
(lower right) in a gap between the cement
paste and a sand particle.
In unrestrained concrete (that is, without any reinforcement), ASR typically
causes the characteristic 'map cracking' associated with ASR, with a repeating
pattern of three radiating cracks 120 degrees apart.
Usually, the best method to confirm that ASR has occurred is to examine the
concrete in either thin section using a petrographic microscope, or in polished
section using a scanning electron microscope (SEM). Gel may be seen in cracks
and in aggregate particles.
The process of alkali-silica reaction is believed to be broadly similar to the
pozzolanic reaction, as occurs normally in concrete containing fly ash, for
example. However, there are important differences.
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In the pozzolanic reaction where a pozzolan is used as a partial cement
replacement, the particles are small. As there is much calcium available in young
concrete, the alkali-silicate gel forms in a thin layer around the pozzolanic
particle and quickly converts to C-S-H and no expansion results.
In the case of alkali-silica reaction, the reaction usually occurs much later,
possibly years after the concrete was placed. Large aggregate particles (large,
that is, compared with cement-sized pozzolan) generate a significant volume of
gel, which then takes up water and expands within the hardened, mature,
concrete.
Because the concrete is mature, calcium availability is limited, as most of the
calcium is bound up in stable solid phases. The rate of supply of calcium is
therefore insufficient to convert the gel quickly to C-S-H, especially if the gel has
formed within an aggregate particle such as opal or chert, where calcium is
scarce.
Figure 9.6 This is the same image as in Figure 9.5, with X-ray spectra superimposed
showing how alkali-silica gel composition changes with time to become more like that of
the surrounding calcium silicate hydrates. At A the gel spectrum shows large peaks due to
silicon and potassium and only a very weak peak due to calcium. At B the calcium peak
has become much stronger and the potassium peak much weaker. At C the potassium
peak has disappeared entirely and the gel has approximately the same composition as the
normal calcium silicate hydrate comprising the bulk of the cement paste. Clearly, the gel is
older with increasing distance from the aggregate particle in which it originated - the
'oldest' gel has had more time in which to take up calcium from the surrounding paste,
and has now become calcium silicate hydrate.
Expansion of the gel as water is taken up, is likely to result in damage to the
surrounding concrete. Over time, the gel will slowly take up calcium and
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eventually the composition of the gel may become similar to that of the calcium
silicate hydrate in the cement paste (see Figure 9.6). By then, though, the
concrete may already be severely damaged.
Conditions necessary for ASR and how to limit expansion
Three conditions are necessary for ASR to occur in concrete:
# A sufficiently high alkali content of the cement pore fluid.
# A reactive aggregate, such as chert.
# Water - needed for the gel to expand; expansion due to ASR will not occur
if there is no available water in the concrete.
Given these three conditions, ways in which we can prevent expansion in
concrete due to ASR may appear obvious; we avoid using reactive aggregates
and we limit the available alkalis. However, restrictions that are too severe will in
themselves cause other problems.
Restricting the alkali in the cement
The cement is usually the main source of alkali in the pore fluid in concrete,
derived from alkali sulfate and from alkalis in the main clinker minerals, mainly in
belite and aluminate. So if we restrict the alkali content of the cement, wont that
limit the alkali in the pore fluid? Yes, it will, but this does not allow for different
cement contents in concrete, so simply imposing a limit on cement alkalis is not a
complete answer to the problem. Also, we need to remember that higher alkali
cements tend to give better early concrete strengths; alite and belite hydrate
faster as pore fluid alkalinity increases.
Imposing limits on cement alkali content that were too low (however defined)
may therefore affect cement performance. It would also increase the cost of
cement production, as bypass dust and precipitator dust high in alkalis could not
be returned to the kiln and would have to go to landfill. Additionally, some raw
materials high in alkali could not be used and would have to be replaced by
possibly more expensive alternatives. So, although restricting the cement alkali
content makes an important contribution to controlling ASR in concrete where
potentially reactive aggregate is to be used, it is not necessarily a complete
answer to the problem.
Alkali limits are usually expressed as sodium equivalent. This conveniently
combines the potassium and sodium oxides, and is useful for other purposes as
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well. Sodium oxide equivalent is defined as: Na2Oeq=(Na2O+0.658K2O)
1
.
Upper limits for sodium oxide equivalent on low alkali cement are typically of the
order of 0.60%-0.75%; check the standards or codes of practice applicable to
your location.
Restricting the alkali in the concrete
An alternative approach is to limit the alkali content of the concrete. This would
then take into account that different concretes have different cement contents.
Limiting the alkali content can be achieved by using lower alkali Portland cement,
by using a lower cement content in the concrete or by partially replacing the
Portland cement with slag, fly ash or microsilica.
The use of slag or a pozzolan in the concrete mix as a partial cement
replacement can reduce the likelihood of ASR occurring as these reduce the
alkalinity of the pore fluid. Slag, fly ash, microsilica and metakaolin have all been
found in various studies to reduce or prevent expansion due to ASR. However,
this is a complex area because some of these cement replacement materials also
contribute alkali when they react.
For example, using some typical Figures from Taylor, fly ash typically contains
1.5% Na2O and 4.2% K2O (1) and slag contains approximately 0.4% Na2O and
0.7% K2O (2). Compared with the alkali levels in Portland cement, slag is
therefore broadly similar and fly ash is considerably higher. However, both are
less reactive than Portland cement and even in mature concrete some slag or fly
ash will remain unreacted.
Only the reacted fraction of the slag or fly ash will have released alkali into the
pore fluid. As this proportion is not known precisely, and anyway will vary
between different concrete mixes, it is difficult to calculate just how much alkali
from the slag or fly ash has become available for reaction. National Rules will
determine what substitution levels are effective and what allowance to make for
slag or PFA alkalis.
Restricting the water
Can we restrict water availability? In most cases, not really, unless the concrete
is entirely under cover and will never get wet. While expansion due to ASR is
unlikely in concrete that remains dry inside buildings, even building interiors can
become saturated in flood conditions. In any case, most concrete is used in
foundations, roads, bridges or other open structures where it will be exposed to
water.
1
The constant 0.658 is derived from the ratios of atomic weights of sodium and
potassium oxides: Na 22.99; K 39.10; O 15.99; therefore Na2O (22.99 x
2)+15.99=61.97; K2O (39.10 x 2)+15.99=94.19; 61.97/94.19 = 0.658.
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Tests for aggregate reactivity
If concrete does not contain reactive aggregate, it follows that there will be no
expansion due to ASR. So, can we prevent expansion by not using reactive
aggregate in concrete? Yes, we can, but we need to decide what we mean by
reactive and we also need some method by which we can determine whether or
not a particular aggregate is reactive.
With some aggregates, expansion due to ASR increases broadly in proportion
with the amount of reactive aggregate in the concrete. The majority of
aggregates (eg: chert) show what is called a pessimum effect; if the proportion
of reactive aggregate in test mixes is varied while other factors are kept
constant, maximum concrete expansion occurs at a particular aggregate content.
Higher or lower proportions of reactive aggregate will give a lower expansion.
In some areas, chert represents the bulk of aggregate used in concrete, with no
resulting expansion due to ASR because the proportion of chert in the concrete is
well above the pessimum. If we excluded all potentially reactive aggregate, we
would not be able to use chert, but such a restriction is unnecessary since it can
clearly be used safely. We just need to avoid aggregate that contains chert near
the pessimum proportion.
There are broadly three types of test for alkali reactivity of aggregate:
# Examination in thin-section using optical microscopy (ie: petrography)
# Chemical tests (eg: immersion in an alkaline solution such as sodium
hydroxide)
# Expansion tests using mortar bars or concrete prisms
Variations on all three of these approaches have been described in different
standards.
Standard microscopy procedures include: ASTM C295-08 Standard Guide for
Petrographic Examination of Aggregates for Concrete and British Standard
BS 812: Part 104: 1994 Testing aggregates - method for qualitative and
quantitative petrographic examination of aggregates.
Chemical tests include ASTM C289 - 07 Standard Test Method for Potential Alkali-
Silica Reactivity of Aggregates (Chemical Method).
Expansion tests include ASTM C227-03 Standard Test Method for Potential Alkali
Reactivity of Cement-Aggregate Combinations (Mortar-Bar Method) and British
Standard BS 812: Part 123: 1999 Testing aggregates - method for determination
of alkali-silica reactivity concrete prism method.
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Petrographic examination of aggregate is widely used and is an effective
diagnostic test, assuming of course that the microscopist is able to recognise
potentially reactive forms of silica and also that the sample examined is
representative of the aggregate as a whole.
Chemical tests can also be effective in identifying potentially reactive aggregate
but may not be a good predictor of expansion where the aggregate shows a
pessimum effect.
Conventional expansion tests with mortar bars or concrete prisms are the closest
simulation to real concrete but may require two years or more to show results;
this may not always be convenient. Accelerated expansion tests can shorten this
timescale but do not simulate real conditions as closely.
In summary, all these tests for aggregate reactivity can be very useful indeed
essential - but all have potential problems and the perfect test for ASR
susceptibility has yet to be developed.
So, is it practicable to limit expansion due to ASR?
Yes, definitely. Despite the limitations weve looked at above, the incidence of
expansion due to ASR has declined markedly over the last 10-20 years where
these different approaches to limiting expansion have been applied. For example,
in the UK, there have been no reported cases since the current rules were
introduced in the 1980s. Generally, codes of practice and national standards
define how these approaches are used in practice in different parts of the world.
Usually, several strategies to limit expansion are applied at the same time.
For example, aggregate producers will routinely have their aggregate examined
petrographically to determine the rock types and their potential reactivity. These
aggregates then go into concrete that contains cement that has limits on alkali
content specifically to minimise the risk of ASR; the concrete may well also
contain fly ash or slag or other mineral addition to limit the available alkali.
Of course, these relatively recent ways of dealing with the problem only control
the problem in concrete produced using these methods. Instances of ASR still
occur in some older concrete because there were fewer controls over what was
used to produce it. Even where good controls are apparently in place, there is
always the potential for things to go badly wrong.
9.1.2 Alkali-carbonate reaction
Alkali-carbonate reaction (ACR) is an expansive reaction between the alkaline
pore fluid in concrete and some aggregates in which dolomite is present. Many
aggregates containing dolomite do not give rise to ACR. Dolomite is a mineral
composed of calcium magnesium carbonate (CaMg(CO3)2). Dolomite is often
present in limestone; while limestone is usually composed mainly of calcium
carbonate (calcite, CaCO3), some limestones also contain dolomite and these are
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known as dolomitic limestones. Other aggregate types may also contain
dolomite.
The reaction is also known as de-dolomitization and occurs between dolomite in
aggregate and hydroxyl ions in the pore fluid. This forms calcium carbonate and
magnesium hydroxide, and releases carbonate into the pore fluid:
CaMg(CO3)2 + 2OH
-
! CaCO3 + Mg(OH)2 +CO3
2-
The dissolved carbonate can then react with calcium hydroxide to form calcium
carbonate, releasing hydroxyl ions into the pore fluid, which can then react with
more dolomite:
CO3 + Ca(OH)2 ! CaCO3 + 2OH
-
ACR was first identified in Canada and has also been confirmed in China and the
Middle East (and probably other places too) but it is rare overall in comparison
with ASR.
There is some difference in emphasis in the literature regarding expansion due to
ACR, including whether the dolomite has to be argillaceous dolomite for the
reaction to occur and also just how expansive the de-dolomitization process
actually is. Also, some people have attributed the expansion to the swelling of
the argillaceous component of the aggregate rather than to de-dolomitization. A
further complication arises if the aggregate also contains alkali-reactive silica as
this may produce alkali-silica reaction; both ACR and ASR may occur in the same
aggregate.
Identification of ASR and ACR
In unrestrained concrete (where no reinforcement is present), expansion from a
point source characteristically causes the typical map-cracking often observed
in association with ASR. However, if reinforcement is present, the crack pattern
will be altered.
In any case, the most reliable method of identifying ASR or ACR is microscopic
examination of the concrete. Typically, cores are taken from the concrete for
petrographic examination using either a petrographic microscope to examine thin
sections of the concrete, or by SEM examination of polished sections of pieces of
the concrete.
9.2 Sulfate attack in concrete and mortar
Concrete and mortar made with Portland cement can be damaged when exposed
to solutions containing sulfate. Groundwater often contains sulfate, and so the
foundations of buildings and other structures are frequently where damage due
to sulfate attack is found. Most of what follows refers particularly to concrete;
sulfate attack in mortar is discussed in Chapter 9.2.4.
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The majority of instances of sulfate attack have two main effects on the cement
paste:
# Sulfate reacts with hydrated aluminate phases, particularly monosulfate
phase, and any unreacted aluminate (C3A), to produce ettringite.
Ettringite formation within the paste exerts an expansive force, causing
cracking.
# Calcium hydroxide (CH) in the paste supplies calcium to produce the
ettringite; when CH becomes scarce, the required calcium for continued
ettringite formation is supplied by the C-S-H, which becomes partly
decalcified.
The need for additional calcium (and water) to form ettringite from monosulfate
is shown by the following equation:
C3A.CaSO4.12H2O + 2Ca
2+
+ 2SO4
2+
+
20H2O ! C3A.3CaSO4.32H2O
(monosulfate) + (2 calcium ions) + (2 sulfate ions) + (20 water molecules) ! (ettringite)
To recap: the cement paste is weakened because calcium to make ettringite is
provided by the CH and decalcified C-S-H. The sulfate is provided by the source
of sulfate that is causing the sulfate attack, eg: ingressing groundwater
containing dissolved sulfate.
We therefore typically have two processes occurring at the same time. Cracking
is generally due to the expansive pressure caused by the growth of ettringite
within the cement paste. Weakening of the paste by decalcification of the calcium
silicate hydrate (C-S-H) that gives concrete its strength, causes further damage.
Eventually, the concrete disintegrates.
Usually, sulfate attack involves a deterioration of the cement paste in the
concrete with the aggregate taking no part in the reaction. However, occasionally
the aggregate can be the cause of the problem if it contains soluble forms of
sulfate (eg: gypsum).
Sulfate attack causes expansion and cracking, and a general loss of concrete
strength, with ettringite often widespread within the cement paste in affected
areas. However, the quantity of ettringite that can form is limited by the available
alumina from the cement. When this is exhausted, gypsum may form if there is a
continued supply of sulfate; gypsum formation also requires additional calcium,
obtained from CH or C-S-H decalcification, and the deterioration of the cement
paste continues.
Sulfate attack can be 'external' or 'internal'.
External sulfate attack is due to penetration of sulfates in solution into the
concrete from outside.
Internal sulfate attack occurs when a source of soluble sulfate is incorporated
into the concrete at the time of mixing, an example might be the presence of
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gypsum particles in the aggregate.
9.2.1 External sulfate attack
This is the more common type and typically occurs where water containing
dissolved sulfate penetrates the concrete. A fairly well-defined reaction front can
often be seen in polished sections; ahead of the reaction front the concrete is
normal, or near normal. Behind the reaction front, the composition and
microstructure of the concrete will have changed. These changes may vary in
type or severity but commonly include:
# Extensive cracking
# Expansion
# Loss of bond between the cement paste and aggregate
# Alteration of paste composition, with monosulfate phase converting to
ettringite and, in later stages, gypsum formation.
The effects described so far are typical of attack by solutions of sodium sulfate or
potassium sulfate. Solutions containing magnesium sulfate are generally more
aggressive, for the same concentration. This is because the magnesium also
takes part in the reactions, replacing calcium in the solid phases with the
formation of brucite (magnesium hydroxide) and magnesium silicate hydrates.
The displaced calcium precipitates mainly as gypsum.
Sources of sulfate, other than groundwater already mentioned, which can cause
sulfate attack include:
# Seawater - typically contains about 0.27% sulfate as SO4.
# Oxidation of sulfide minerals in clay adjacent to the concrete: this can
produce sulfuric acid, which then reacts with the concrete.
# Bacterial action in sewers: anaerobic bacteria produce sulfur dioxide,
which dissolves in water and then oxidises to form sulfuric acid.
# Pollution from industrial waste.
# In masonry, sulfates are present in some bricks and can be gradually
released over a long period of time, causing sulfate attack of the mortar,
especially where sulfates are concentrated due to moisture movement. For
this reason, the soluble salt content of bricks in many countries is limited
by national standards.
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Deleterious processes in concrete
Figure 9.7 SEM image of sulfate attack in
concrete; ettringite has replaced C-S-H
within the marked areas.
Figure 9.8 SEM image of sulfate attack in
concrete; here, ettringite (examples - e) has
largely replaced C-S-H throughout this field of
view.
9.2.2 Internal sulfate attack
This can occur when a source of sulfate in sufficient quantity is incorporated into
the concrete when mixed. Examples include the use of sulfate-rich aggregate,
excess of added gypsum in the cement, oxidised sulfide minerals in the
aggregate, or contamination. Proper screening and testing procedures should
generally avoid internal sulfate attack.
Delayed ettringite formation
Delayed ettringite formation (DEF) is a special case of internal sulfate attack. A
key point in understanding DEF is that ettringite is destroyed by heating above
about 70
C.
DEF occurs if ettringite that formed normally during hydration is decomposed
through heating, but then subsequently re-forms in the hardened concrete.
Delayed ettringite formation has been a significant problem in many countries. It
typically occurs in concrete that was cured at elevated temperatures, for
example, where steam curing has been used - it was originally identified in
steam-cured concrete railway sleepers (railroad ties). It can also occur in large
concrete pours where the heat of hydration has resulted in high temperatures
within the concrete. DEF may also occur in older concrete subjected to heating
(eg: due to fire).
DEF causes expansion of the concrete due to expansive ettringite formation
within the paste and it can cause serious damage to concrete structures. DEF
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normally arises from the sulfate in the cement and may occur some time
months or years after the concrete was placed.
In normal concrete where no sulfate ingress has occurred, the total amount of
ettringite that forms as the result of DEF is evidently limited by the sulfate
contributed by the cement initially. It follows that the quantity of ettringite
forming due to DEF is relatively small. Ettringite crystals form widely-dispersed
throughout the paste. If expansion due to DEF causes cracking, this is
particularly likely around aggregate particles; ettringite may subsequently form
in the cracks but this does not necessarily mean the ettringite in the cracks was
the cause of the initial cracking.
DEF causes a characteristic form of damage to the concrete. While the paste
expands because ettringite crystals are forming within it, the aggregate does not
expand. Consequently, gaps form around these non-expanding 'islands' of
aggregate within the paste (Figures 9.9-9.11). Often, these peripheral gaps
become filled with ettringite (Figure 9.11).
Figure 9.9 Two-dimensional representation
of DEF expansion; at A the blue cement
paste is in contact with the red aggregate. At
B, the blue paste has expanded uniformly,
but the red aggregate has not. Consequently,
a gap has formed between the aggregate
and the paste.
Once gaps have formed at the periphery of aggregate particles, any further
ettringite formation is likely to occur within these gaps, where it can form freely,
rather than within the paste where the crystals would have to exert an expansive
force in order to create space in which to crystallise.
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Figure 9.10 DEF expansion: SEM image
showing a limestone particle with a gap
between the limestone and the cement paste
(arrowed).
Figure 9.11 DEF expansion: SEM image
showing ettringite (e) filling a gap between
a limestone aggregate particle (L) and the
cement paste. Small silica sand grains (s)
remain bonded to the cement paste and do
not show peripheral gaps.
The images in Figures 9.10 and 9.11 are characteristic of damage to concrete
due to DEF. Where peripheral gaps form around aggregate particles, the
aggregate is no longer contributing to concrete strength, since it is effectively
detached from the cement paste. Often, these gaps become filled with ettringite;
the ettringite does not form a strong bond between the paste and aggregate and
so the concrete is still weakened.
Conditions necessary for DEF to occur are:
# High temperature (>70 "C approx.), usually during curing but not
necessarily.
# Water - intermittent or permanent saturation after curing. An ettringite
molecule contains 32 molecules of water so ettringite formation evidently
requires wet conditions.
The effect of cement composition on DEF is not well understood. Some factors
correlate strongly but the causes are not clear. In laboratory tests, DEF expansion
has been shown to correlate positively with cement-related factors, including:
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# high sulfate
# high alkali
# high MgO
# cement fineness
# high C3A
# high C3S
A pessimum cement sulfate content of 4%, at which maximum expansion occurs,
has been suggested (3); this sulfate level is higher than permitted in some
national standard specifications for cement. Composite cements tend to show
good resistance to DEF.
In laboratory tests, limestone coarse aggregate has been found to reduce
expansion, although, as shown in Figures 9.8-9.9, the use of limestone aggregate
does not confer immunity. In general, careful control of curing temperature has
proved to be a reliable precaution against DEF.
Expansion due to DEF and ASR have been linked; in one study, initial expansion
due to ASR was enhanced by subsequent expansion due to DEF (4).
From the above, you will probably have guessed that delayed ettringite formation
is not fully understood.
9.2.3 Thaumasite form of sulfate attack (TSA)
The thaumasite form of sulfate attack (often abbreviated to TSA) requires
sources of sulfate and carbonate. Thaumasite occurs as a natural mineral as an
alteration product of limestone, although it is rare.
Thaumasite can form in both concrete and mortar. The normal cement hydration
products, mainly calcium silicate hydrate and calcium hydroxide, are decomposed
as a result of both sulfate attack and of carbonation. Thaumasite itself is a weak
and friable mineral, so when it replaces the calcium silicate hydrate, the concrete
is severely weakened.
Thaumasite has the chemical formula:
[Ca3Si(OH)6.12H2O] (SO4)(CO3)
or
CaSiO3.CaCO3.CaSO4.15H2O
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It tends to form at low temperatures, typically about 4 C - 10 C. As it forms,
the concrete or mortar converts to a friable material, often described as a
mush. Concrete severely affected by thaumasite formation can easily be broken
with the fingers and the coarse aggregate lifted out.
A source of additional water is also required for thaumasite formation. Damp
cementitious render over brickwork, especially where the render is cracked, and
concrete and masonry in cool, damp cellars are typical examples of where
thaumasite may occur.
Normal sulfate attack usually results in the formation of ettringite. This uses
aluminium provided by the cement and clearly this is limited in quantity in
normal concrete. However, thaumasite formation does not involve aluminium;
given an adequate supply of sulfate and carbonate, thaumasite can continue to
form until the calcium silicate hydrate is completely decomposed. Consequently,
while the use of sulfate-resisting Portland cement provides some defence against
normal sulfate attack, it does not give any particular protection against
thaumasite formation.
Sulfate can be supplied from a range of sources; groundwater or bricks are
common examples, or oxidation of sulfide aggregate. Carbonate can be supplied
from atmospheric CO2 or from limestone present in the concrete or mortar.
Serious damage in concrete due to thaumasite formation is not common, even in
cool, damp climates, but it can occur.
Figure 9.12 Polished section showing degraded
concrete containing white crystalline thaumasite
formed around coarse limestone aggregate (large
dark particles) and in cracks. Examples of thaumasite
are arrowed. This polished section was 40mm in
diameter but thaumasite formation is so extensive
that it requires little magnification to be clearly
visible.
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Deleterious processes in concrete
9.2.4 Sulfate attack in mortar
Sulfate attack in mortar can be due to similar causes as sulfate attack in
concrete. Sources of sulfate are typically the cement in the mortar, sulfate in
bricks or stone and sulfate in groundwater, or a combination of these sources.
Damage in mortar, or render, can be due to expansive ettringite formation,
causing loss of bonding between cement paste and sand, and between the
cement paste and the brick or stonework. The mortar becomes friable, with
cracking and scaling readily visible. Often, however, ettringite is present in voids
in masonry, where it causes little or no damage; air-entrained mortar contains
numerous voids in which ettringite can form without exerting an expansive force.
Efflorescence (Chapter 9.7) may be associated with sulfate attack, with white
crystalline growth on the surface of the damaged masonry or render.
Damage to mortar, and masonry generally, can be due to the formation of
crystals of sodium, potassium or magnesium sulfate within the mortar, brick,
stone or render; these can exert an expansive force on crystallisation and
damage may be severe. Magnesium sulfate can be especially damaging.
Damage due to thaumasite formation in masonry can occur, especially in cold,
damp conditions where there is also a source of carbonate. The carbonate may
be present in cement, stone or groundwater. TSA in masonry typically occurs in
cold, wet conditions such as cellars in cool climates, or foundations.
DEF would not normally be expected to occur in mortar unless the mortar had
been heated by an external source; the heat of hydration of the cement would
normally be dissipated by the bricks or stone.
9.2.5 Identification of sulfate attack
Severe damage to concrete and mortar can be readily identified from visual
inspection. A range of different analytical techniques can be used to confirm that
sulfate attack has occurred. A calculation of the cement content by chemical
analysis, together with a determination of the sulfate content, can indicate that it
may have occurred if the sulfate content is appreciably higher than would be
expected from sulfate normally present in the cement. This is perhaps the
simplest test, although it is not conclusive - for example it would not normally
indicate that DEF had occurred, since sulfate will probably not be present in
excess.
X-ray diffraction may indicate the presence of gypsum and ettringite, or
thaumasite; if present in appreciable amounts, sulfate attack is likely to have
occurred.
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Deleterious processes in concrete
Generally, the best technique for identifying sulfate attack is microscopic
examination of concrete cores. This could be a petrographic examination of the
concrete in thin-sections, or by scanning electron microscopy (SEM) and X-ray
microanalysis using polished sections.
9.3 Carbonation
Although included in this chapter on deleterious processes, not all of the effects
of carbonation on concrete are bad. It increases concrete density and so reduces
permeability. Carbonation is associated with the corrosion of steel reinforcement
and with shrinkage but it also increases both the compressive and tensile
strength of concrete.
Carbonation occurs when carbon dioxide dissolves in the pore fluid of the
concrete to produce carbonate ions. These react with calcium to produce calcium
carbonate, usually in the form of calcite, although aragonite can form in hot
conditions.
Because the process involves dissolved carbon dioxide, a film of pore fluid on the
hydration products in the concrete is necessary for carbonation to occur. As
carbonation proceeds, calcium is supplied by the calcium hydroxide in the cement
paste, and also by the calcium silicate hydrate (C-S-H). Calcium hydroxide is
depleted and the ratio of calcium to silicon in the C-S-H decreases. In fully
carbonated cement paste, most of the calcium is present as calcium carbonate.
The C-S-H has lost its calcium and is now an impure silica gel, also containing
aluminium from other cement hydration products and sodium and potassium
from the pore fluid (Figure 9.13).
Saturated concrete carbonates slowly, because the capillary pores in the concrete
are full of water and this inhibits further ingress of water or gas. In permanently
dry conditions, carbonation proceeds slowly or not at all, as there is not enough
water in contact with the hydration products.
Normal wetting and drying of concrete produces conditions conducive to
carbonation, especially by rainwater containing dissolved carbon dioxide, but
carbonation proceeds most rapidly under humid but non-saturated conditions,
with a relative humidity of 50%-70%.
The surface of fresh concrete carbonates very quickly, within a few hours or days,
but the depth to which the concrete is carbonated is, at first, very limited -
perhaps only a few microns.
Over time, the carbonation front gradually moves further into the concrete.
After a year, the distance from the surface that the carbonation front has reached
may be 1 mm to perhaps 5 mm, depending on the permeability of the concrete.
Dense, impermeable, concrete made with a low water/cement ratio will carbonate
much more slowly than porous concrete made using a high water/cement ratio.
Carbonate ions have to travel a greater distance from the surface to the
carbonation front as the carbonation depth increases. Consequently, the rate of
progress into the concrete of the carbonation front gradually slows.
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Deleterious processes in concrete
Figure 9.13 SEM image of polished section of
concrete roof tile, approximately one year old. The
carbonation depth can be seen from the grey-level
change of the cement paste at a depth of about
50!m from the surface (arrowed).
The depth of the carbonated zone in concrete - often abbreviated to the
carbonation depth - can be measured from the image above, but making a
polished section and using a microscope is a complicated process just to make a
rapid test. A much easier way is to use an indicator sensitive to a suitable pH
value.
Phenolphthalein indicator is commonly used to measure carbonation depth and is
available from chemical suppliers. Phenolphthalein is a white or pale yellow
crystalline material. For use as an indicator it is dissolved in a suitable solvent
such as isopropyl alcohol (isopropanol) in a 1% solution. The indicator solution is
a clear liquid but turns purple above a pH of about 8.5.
If you apply phenolphthalein indicator to concrete and it quickly turns purple, the
concrete pore fluid is strongly alkaline. In Figure 9.14, the carbonation depth
shown by this rapid test is clearly about 5mm-7mm. The only tools needed are
the indicator liquid and a hammer and perhaps a cold chisel to fracture the
concrete.
The phenolphthalein indicator solution is applied to a fresh fracture surface of
concrete. If the indicator turns purple, the pH of the concrete pore fluid is above
8.5. Where the solution remains colourless, the pH of the concrete is below 8.5,
suggesting carbonation. A fully-carbonated paste has a pH of about 8.4. In
practice, a paste with a pH of 8.5 may only give a faintly discernible slightly pink
colour. A strong, immediate, colour change to purple suggests a pH that is rather
higher, perhaps pH 9 or 10.
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Deleterious processes in concrete
Figure 9.14 Fresh fracture surface through a
concrete slab, with phenolphthalein indicator solution
applied. The indicator has not changed colour near
the top and bottom surfaces, suggesting that these
near-surface regions are carbonated to a depth of at
least 5 mm from the top surface and 7 mm from the
lower surface. Where the indicator has turned purple
- the centre of the slab - the pH of the concrete pore
fluid remains high (above 8.5, probably nearer 10).
Whether the cement paste here is completely
uncarbonated is unclear, despite the strong purple
indicator colour; a more complete assessment would
require microscopic examination.
Warning: both phenolphthalein itself and isopropyl alcohol are harmful
and, since it contains alcohol, the indicator solution is flammable.
Ingestion, or contact with skin or eyes should be avoided, as should
breathing the vapour. Possible effects on the human body include cancer
and damage to kidneys and the central nervous system. For more
information, do an internet search for something like: phenolphthalein
indicator hazard. For example, see:
http://fscimage.fishersci.com/msds/45376.htm.
Obviously, the phenolphthalein test is rather crude, but its simplicity makes it
very useful. It is important to make sure the concrete surface being tested is a
freshly-fractured surface; testing an old surface wont tell you anything as it will
have started to carbonate. Ideally, you would break the concrete (or take mini-
cores or use drilling dust) then test it immediately.
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The carbonation depth is proportional to the square root of time
d=k"t
where d is the carbonation depth, t is time and k is a constant of proportionality.
Occasionally, this can be quite useful. Suppose you find that a piece of concrete
that you know to be nine years old has a carbonation depth of 12 mm; for that
piece of concrete in that particular environment, k is therefore 4.
You can then work out the likely carbonation depth at any other time; after three
months it was only 2 mm and after 100 years it will be 40 mm. Dont expect this
relationship between time and carbonation depth to work perfectly. All things
being equal, it should work well. However, in cement and concrete all things are
never equal. Measurement of carbonation depth is imprecise because of
distortions in the carbonation front due to factors such as aggregate, microcracks
and local variations in concrete porosity. Also, the carbonation depth may be
affected locally by wind direction, nearby sources of carbon dioxide (eg: road
traffic) and probably a myriad of other factors.
Also, while the use of phenolphthalein indicator is straightforward and a very
useful test, things are actually a bit more complicated when examined in more
detail.
Normal concrete pore solution is saturated with calcium hydroxide and also
contains sodium and potassium hydroxide; the pH is typically pH 13-14. Concrete
with a pore solution of pH 10-12 is less alkaline than sound concrete, but would
still produce a strong colour change with phenolphthalein indicator. It therefore
follows that the indicator test is likely to underestimate the depth to which
carbonation has occurred, as will be seen below.
Optical microscopy or scanning electron microscopy often show indications of
early-stage carbonation even where the phenolphthalein indicator changes colour
to purple. Microscopy shows a gradual transition between concrete near the
surface that is fully carbonated, and concrete at depth that is entirely normal and
uncarbonated.
As an example, Figure 9.15 shows a montage of SEM images of a polished
section from the same concrete slab as the piece shown in Figure 9.14. The
montage extends to a depth of about 7 mm from the surface.
The concrete appears intensely carbonated to a depth of about 4 mm, where
there is a distinct change in the appearance of the paste. Less than 4 mm from
the surface, very little unhydrated cement remains and the paste has converted
almost entirely to calcium carbonate and impure silica gel (see Inset A, 250 !m
depth).
Below about 4 mm depth, unhydrated cement particles remain and the paste
microstructure has not obviously altered greatly from its normal, high-alkaline,
state (Inset B, 7 mm depth). However, even here, the paste appears slightly
altered, becoming a little denser and with a loss of calcium hydroxide (compare
with the image in Figure 6.5).
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The concrete mid-way through the slab is shown in Figure 9.16. Even here, there
are signs of slight carbonation. X-ray microanalysis of the C-S-H would show a
slight increase in the Si/Ca ratio.
This particular example of concrete paving is clearly porous and permeable.
Microscopy shows indications of carbonation throughout the thickness of the slab,
even though phenolphthalein indicator showed the central region to be
uncarbonated (Figure 9.14). The pH at the slab centre is probably above pH10
(as shown by a rapid colour change on application of the indicator solution) but
below pH13-14 as is normally present in uncarbonated concrete. Denser concrete
would have much smaller carbonation depths and the interior would remain
unaffected by carbonation. The concrete roof tile in Figure 9.13 is an extreme
example in the other direction; after about one year, the dense paste has limited
carbonation to only a few tens of microns.
Nevertheless, despite its limitations, the indicator test is very useful as a means
of making a quick and easy initial assessment and it is very widely used. Use it,
but be aware of its limitations.
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A: Depth 250!m intensely carbonated
Highly carbonated
~4mm depth
Less carbonated
B: Depth 7mm: less altered by
carbonation than near the surface but
some alteration has still occurred.
See also Figure 9.16.
Figure 9.15 Polished section of concrete from the same slab as in Figure 9.14.
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Figure 9.16 View of slab at a depth of about
15mm approximately at the centre, and
about twice the depth shown in Figure 9.15.
Even here, there are signs of slight
carbonation, with little CH visible and a
densification of the microstructure.
9.4 Steel corrosion
The corrosion of steel reinforcement is probably the single most common form of
concrete deterioration. Its importance is demonstrated by the mountain of
literature on the subject and also by the many enterprises specialising in
sophisticated methods of repairing concrete damaged through steel corrosion.
The following is the briefest of summaries describing the problem.
Steel that has sufficient cover of dense, impermeable, concrete (the cover
zone) should last almost indefinitely, as the alkaline conditions in the concrete
protect it from corrosion. However, the importance of quality control to ensure
adequate cover cannot be overemphasised; porous and permeable concrete,
made with a high water/cement ratio and containing steel near the surface, is
particularly vulnerable to damage.
Normally, a thin layer of iron oxide called the passivation layer around the steel
prevents it from oxidising further. Provided the pH of the pore fluid remains high
(above approximately 11.5), the steel should remain in good condition. However,
if the alkalinity of the surrounding concrete pore fluid falls, as occurs when
concrete carbonates, the passivation layer is lost and the steel corrodes.
The corrosion process is expansive due to the formation of rust. This causes
pressure to be exerted on the surrounding concrete, resulting in cracking and
spalling. Also, the bond between the steel and the surrounding concrete is
weakened or broken and the steel is weakened through becoming thinner. In
addition to damage to the concrete, the benefits of the presence of the steel
reinforcement are therefore also lost.
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The passivation layer is impaired in the presence of chloride, even if the pH
remains high. This effect is particularly important in concrete used in highway
structures where de-icing salt is used, and also in marine environments such as
harbours or sea defences.
The corrosion process is electrochemical, with electrical cells forming due to
variations within the steel or concrete. These variations could be due to small-
scale damage to the steel oxide layer, or to physical or chemical variability within
the concrete.
For corrosion to occur, the steel must be in contact with the pore solution, which
acts as the electrolyte. Oxygen must be also present. This need for oxygen
means that corrosion may not occur in carbonated concrete provided it is
sufficiently dense to restrict the supply of oxygen.
For corrosion to be induced by chloride, the chloride ions have first to penetrate
the concrete. The permeability of the concrete will be important in controlling
how quickly chloride can diffuse through the microstructure and reach the steel.
An additional factor affecting the rate of corrosion is the extent to which the
cement hydration products can bind chloride ions; AFm phase can bind chloride
to form Friedel's salt (C3A.CaCl2.10H2O). Friedels salt is frequently seen when
using scanning electron microscopy and X-ray microanalysis to examine concrete
in polished section that has been exposed to road de-icing salt.
9.5 Leaching
Leaching in concrete is the process by which soluble material is extracted from
the concrete by flowing water. The water may flow over the concrete surface, or
percolate through cracks. Water readily extracts sodium and potassium hydroxide
from the concrete pore fluid, lowering the pH; it also progressively dissolves
calcium hydroxide and decomposes calcium silicate hydrate (C-S-H), ettringite
and AFm phase.
Since it is C-S-H that gives concrete its strength, C-S-H decomposition gradually
reduces the strength of the affected concrete until it disintegrates. Calcium is
leached from the C-S-H, leaving an impure hydrous silica gel. As leaching
progresses, the concrete becomes more porous and permeable (Figure 9.17) and
may also be susceptible to damage by other mechanisms such as frost attack.
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Figure 9.17 SEM image of a polished section
showing concrete that was once dense but is
now highly porous due to the loss of hydration
product due to leaching. Even where the paste
remains, it is clearly porous and weak and
extensively carbonated. Black areas are pores
filled with epoxy resin when the polished
section was prepared.
Dense concrete, made using a low water/cement ratio mix, is obviously likely to
be less affected by leaching than porous concrete made using a high
water/cement ratio mix. Other factors affecting how quickly leaching can damage
concrete include whether the water is hard or soft, water temperature and what
is already dissolved in the water. Concrete exposed to acidic water, such as from
peaty moorland, is particularly at risk.
9.6 Frost damage (freeze-thaw action)
Freezing conditions can damage concrete, particularly where there is a repeating
pattern of freezing followed by thawing. In laboratory tests, the number of
freeze-thaw cycles a particular concrete can undergo before showing signs of
damage is a measure of the concretes ability to withstand frost damage.
The affected concrete surface typically has a rough appearance, with flakes of
concrete gradually becoming detached.
Porous and permeable concrete, made with a high water/cement ratio, is
particularly susceptible to damage. Conversely, dense, impermeable concrete
made with a low water/cement ratio is resistant to damage.
Air entrainment of concrete can greatly improve the resistance of concrete and
mortar to frost damage. A surfactant admixture is used to lower the surface
tension of the pore fluid, resulting in the entrapped air in the concrete being
distributed between myriads of tiny bubbles. These small voids are typically
10!m-200!m in diameter.
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The voids prevent or limit damage by providing space into which the pore fluid
can expand on freezing. To be effective, the voids need to be closely spaced. The
void spacing factor is the average value of the maximum distance from any
point in the paste to the nearest void. Typical values range from 100m -200m
but the void spacing factor necessary to give good frost protection varies from
one concrete to another.
Figure 9.18 Bridge parapet damaged by
frost, Scotland. Note scaling of concrete
surface and exposed aggregate.
9.7 Efflorescence on masonry
Efflorescence often occurs on masonry, especially in damp climates. It does not
usually indicate that sulfate attack has occurred in the sense that physical
damage has been caused.
Most efflorescence is due to soluble salts such as sodium or potassium sulfate on
the surface of new masonry. It normally disappears over the course of a year or
so after construction and any damage is usually aesthetic rather than physical.
The sulfate salts are typically derived mainly from the cement, although brick or
stone may also contribute to efflorescence if they also contain soluble sulfate
salts.
The problem is more likely to occur where bricks have been left unprotected and
are saturated before construction.
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Figure 9.19 Efflorescence on recently-built
wall, south-east England.
Photo courtesy Peter-William Eaves, MRICS.
Occasionally, efflorescence can be of a more persistent form, usually composed of
gypsum or syngenite; once it has appeared on the surface of masonry it is
probably permanent unless removed. It can be associated with the use of non-
standard air-entraining agents in the mortar, such as washing-up liquid (5),
although other causes are possible.
References, Chapter 9
1. Cement Chemistry, H F W Taylor, Thomas Telford, 2nd ed. 1997 p273
2. Cement Chemistry, H F W Taylor, Thomas Telford, 2nd ed. 1997 p263
3. Cement Chemistry, H F W Taylor, Thomas Telford, 2nd ed. 1997 p378
4. S Diamond and S Ong, Cement Technology (Ceramic Transactions, Vol 40,
p79). Eds. Gartner and Uchikawa, American Ceramic Society, 1994.
5. 'Investigation into causes of persistent efflorescence on masonry.' G K
Bowler and N B Winter, Masonry International 11, 1, 1997.
Further reading, Chapter 9
Alkali-silica reaction:
Concrete Society Report TR 30: Alkali-Silica Reaction - Minimizing the risk of
damage to concrete, published by the Concrete Society in the United Kingdom.
Price: 90.00.
BRE Digest 330, 2004: Alkali-silica reaction in concrete: 2004 edition - four part
set.
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Deleterious processes in concrete
Alkali carbonate reaction:
Cement Chemistry, H F W Taylor, Thomas Telford, 2nd ed. 1997, p383.
Leas Chemistry of Cement and Concrete, 4th edition, ed. Peter Hewlett,
Elsevier, 1998, p964.
Delayed ettringite formation:
Lawrence C D Laboratory Studies of Concrete Expansion Arising from Delayed
Ettringite Formation, (1993) published by the British Cement Association.
Lawrence C D (1995) in Cement and Concrete Research, Vol 25, p903.
Kelham S (1996) in Cement and Concrete Composites, Vol. 18, p171.
Steel Corrosion
Cement Chemistry, H F W Taylor, Thomas Telford, 2nd ed. 1997, p360.
Or, for (much) more detail, see:
Corrosion of Steel in Concrete: Understanding, Investigation and Repair, John P
Broomfield, 2006, Published by Taylor & Francis. ISBN-13: 978-0415334044.
Leaching
Cement Chemistry, H F W Taylor, Thomas Telford, 2nd ed. 1997, p380.
Air entrainment
Cement Chemistry, H F W Taylor, Thomas Telford, 2nd ed. 1997 p328.
ASTM C457-09 Standard Test Method for Microscopical Determination of
Parameters of the Air-Void System in Hardened Concrete. ASTM International,
West Conshohocken, PA, USA. Available for download from: www.astm.org. Price
$43.00.
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10Standard Specifications for Portland Cement
Cement is one of the materials fundamental to the infrastructure of the modern
world. In many countries, cement was one of the first materials for which a
standard specification was devised.
For example, one of the first specifications drawn up by the British Standards
Institute after it was formed in 1901 was a standard specification for Portland
cement (BS 12, 1904). Other early specifications were for electric power cables
(BS 7), steel for use in railway lines or railroad tracks (BS 11), tramway and dock
rails and fishplates (BS 2) and steel for steam boilers (BS 14). Such materials
were fundamental to the brave new world of industrial society and so these were
the priorities for quality control.
Cement was fundamental then and it still is, of course. This e-book is not really
about standards but about the principles of how cement works but well just have
a quick look at two important cement standards.
While Portland cement is basically limestone and clay (or other suitable
materials) heated at around 1450 "C, standards for Portland cement differ in
detail. The compositional requirements differ to some extent and the methods of
testing cements for compliance with the standards are also different.
The two principal worldwide standards for Portland cement are: EN 197-1
(Europe) and ASTM C 150 (USA). Additionally, although no longer used in the
United Kingdom, the British Standard BS12: 1996 is still often specified in
international cement trading.
EN 197-1 covers not only Portland cement but also cements containing Portland
cement and other materials. ASTM C150 applies to Portland cement only.
Standard Specifications for Portland Cement
10.1 ASTM C 150-07
The ASTM Portland cement standard current at the time of writing is:
C 150-07 Standard Specification for Portland Cement
Five types of Portland cement are described (Table 10.1), with three more air-
entrained sub-types.
Table 10.1 Portland cement types described in ASTM C150-07.
Type I For use when the special properties specified for any other types
are not required.
Type IA Air-entraining cement for the same uses as Type I, where air-
entrainment is desired.
Type II For general use, more especially when moderate sulfate resistance
or moderate heat of hydration is desired.
Type IIA Air-entraining cement for the same uses as Type II, where air-
entrainment is desired.
Type III For use when high early strength is desired.
Type IIIA Air-entraining cement for the same uses as Type III, where air-
entrainment is desired.
Type IV For use when a low heat of hydration is desired
Type V For use when high sulfate resistance is desired.
Specified constituents of the cement are limited to:
# Portland cement clinker.
# Water or calcium sulfate or both: includes gypsum and other forms of
calcium sulfate and associated bound water; also any other bound water
such as may occur in hydration products if the cement should have
hydrated slightly.
# Limestone, up to 5% by mass.
# Processing additions (small amounts of material to aid in the production or
handling of the cement, eg: grinding aids, kiln dust).
# Air-entraining addition (for air-entraining cements).
Compositional and physical requirements are given for each of the cement types,
with references to appropriate ASTM test methods.
Annex A1 of the standard shows how to calculate the potential cement phase
composition. This calculation allows for the presence of calcium sulfate and
interground limestone by using a modified form of the traditional Bogue
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Standard Specifications for Portland Cement
calculation.
The quantity of limestone in the cement is calculated on the basis of the
measured carbon dioxide content of the cement and of the limestone used. A
sample Mill Test Report is shown, indicating the chemical and physical
requirements of the specification.
Some other cement-related ASTM standards
Cements containing other constituents such as fly ash and slag are specified in:
ASTM C595 / C595M-09 Standard Specification for Blended Hydraulic
Cements
and
ASTM C1157 / C1157M-09 Standard Performance Specification for
Hydraulic Cement
The USA currently uses a lower proportion of composite (blended) cements
compared with Europe or Asia. The performance and environmental benefits of
using composite cements may result in their increased use over time.
Methods of cement analysis are specified in:
ASTM C114-09 Standard Test Methods for Chemical Analysis of Hydraulic
Cement.
Other relevant standards include:
ASTM C109 / C109M - 08 Standard Test Method for Compressive Strength
of Hydraulic Cement Mortars using 2 in. or 50 mm cube specimens
ASTM C115 - 96a (2003) Standard Test Method for Fineness of Portland
Cement by the Turbidimeter
ASTM C183 - 08 Standard Practice for Sampling and the Amount of
Testing of Hydraulic Cement
ASTM C186 - 05 Standard Test Method for Heat of Hydration of Hydraulic
Cement
ASTM C191 - 08 Standard Test Methods for Time of Setting of Hydraulic
Cement by Vicat Needle
ASTM C266 - 08 Standard Test Method for Time of Setting of Hydraulic-
Cement Paste by Gillmore Needles
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Standard Specifications for Portland Cement
10.2 European Standard EN-197
The principal European standard for cements current at the time of writing is:
EN 197-1:2000 Cement Composition, specifications and conformity
criteria for common cements.
This standard covers twenty-seven common cement types available in Europe
under five general headings, including Portland cement.
Cements are specified by both their constituents and by their strength class.
Initially, this looks a bit complicated but all will become clear.
10.2.1 European Standard EN-197, composition
First, we need to look at the cement constituents; these dictate the basic cement
type (Table 10.2).
Table 10.2 Types of cement described in EN 197-1.
Designation Description
CEM I Portland cement, with up to 5% of minor additional constituents (macs)
CEM II Portland-composite cements: Portland cement with up to 35% of other
single constituents, including:
# Portland-fly ash cement (CEM II/A-V, CEM II/B-V)
# Portland-slag cement (CEM II/A-S, CEM II/B-S)
# Portland-limestone cement (CEM II/A-L (LL), CEM II/B-L (LL)
# Portland-silica fume cement (CEM II/A-D)
CEM III Blastfurnace cements: Portland cement with more than 35% blastfurnace
slag:
(CEM III/A, CEM III/B, CEM III/C)
CEM IV Pozzolanic cements Portland cement with more than 35% pozzolana (CEM
IV/A, CEM IV/B)
CEM V Composite cements: Portland cement with more than 35% blastfurnace
slag and pozzolana or fly ash
To be designated as CEM cement of any type containing Portland cement and
additions, the cement has to be factory-produced by either blending or inter-
grinding.
# A CEM I cement contains the maximum amount of cement clinker (up to
100%, less gypsum).
# A CEM I cement is therefore a basic Portland cement.
# CEM II, CEM III, CEM IV and CEM V cements all contain Portland cement
mixed with other materials.
There is also provision for low-heat cements.
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Standard Specifications for Portland Cement
Macs
All types of cement may contain up to 5% macs. Macs are minor additional
constituents. Typical examples of macs are fine limestone, kiln dust or fly ash. A
cement containing a mac is considered for specification purposes to be the same
as if the mac were not present and the cement has to meet the same
performance criteria.
For example, a CEM I cement is a Portland cement. A CEM I cement with 5%
limestone as a mac is also a Portland cement and should have the same
characteristics for setting time, strength, soundness and composition as if the
mac were not present.
Codes
Other than for CEM I, the following codes are necessary in order to interpret the
cement types:
# The suffix A means a low level of addition of the mineral addition and the
suffix B means a high level of mineral addition (Table 10.3). For CEM III
blastfurnace cements, suffixes A, B and C indicate increasing proportions of
slag.
# For the CEM II cement type, codes for the second main constituent are
specified as follows:
S blastfurnace slag
D silica fume
P natural pozzolana
Q natural calcined pozzolana
V siliceous fly ash
W calcareous fly ash
L or LL limestone (LL means high-purity limestone)
T burnt shale
M two or more of the above
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Standard Specifications for Portland Cement
Table 10.3 EN 197-1 CEM II cements: these are some of the more common
cement types.
Designation Name Second main
constituent
% Second
main
constituent
% Clinker
CEM II/A-S Portland-slag
cement
Blastfurnace
slag
6-20 80-94
CEM II/B-S Portland-slag
cement
Blastfurnace
slag
21-35 65-79
CEM II/A-D Portland-silica
fume cement
Silica fume 6-10 90-94
CEM II/A-V Portland fly-
ash cement
Fly ash 6-20 80-94
CEM II/B-V Portland fly-
ash cement
Fly ash 21-35 65-79
CEM II/A-L (or
-LL)
Portland-
limestone
cement
Limestone 6-20 80-94
CEM II/B-L (or
LL)
Portland-
limestone
cement
Limestone 21-35 65-79
As will be inferred from the list of codes for the second CEM II constituent, the
list of cement types in Table 10.3 is not complete; the cements shown are the
more common types but there are others specified in the standard, containing for
example, calcareous fly ash or burnt shale.
10.2.2 European Standard EN-197, strength classes
Cements are also specified according to their strength class. Three standard
strength classes are defined, based on the minimum 28-day mortar prism
strength:
32,5
42,5
52,5
(NB: The use of the comma is part of the specification; units are MPa.)
Additionally, early strength development is indicated by a suffix:
L: Low early strength
N: Normal early strength
R: High early strength
The minimum and maximum strengths of the three strength classes are shown
below (Table 10.4).
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Standard Specifications for Portland Cement
Table 10.4 EN 197-1 cement strength classes for all CEM cements.
Strength
class
Minimum
2-day strength
Minimum
7-day
strength
Minimum
28-day
strength
Maximum
28-day
strength
32,5 N - 16 32,5 52,5
32,5 R 10 - 32,5 52,5
42,5 N 10 - 42,5 62,5
42,5 R 20 - 42,5 62,5
52,5 N 20 - 52,5 -
52,5 R 30 - 52,5 -
For example, a bag of cement labelled:
CEM I 52,5 R
is a high early strength Portland cement producing at least 52.5 MPa at 28 days
and at least 30 MPa at 2 days, based on mortar prism strength tests.
Two more examples:
CEM II/A-LL 42,5N: this is a Portland composite cement with a low proportion of
the second constituent (the A), the second constituent being high-purity
limestone (the LL). The proportions would be 80%-94% Portland cement clinker
and 6%-20% high-purity limestone. The cement is classed as producing normal
strength development (the N): at least 42.5 MPa at 28 days and at least 10
MPa at 2 days, based on mortar prism strength tests.
(CEM II/B-V 32,5R): this is a Portland composite cement with a high proportion
of the second constituent (the B), the second constituent being siliceous fly
ash. The proportions would be 65%-79% clinker and 21%-35% fly ash. The
cement is classed as producing rapid strength development, at least 10 MPa at 2
days, and at least 32.5 MPa at 28 days, based on mortar prism strength tests.
There are additional low early strength classes for CEM III cements covered by
EN 197-4:2004.
Although the system may appear complex, the combination of the cement
designation and the strength class conveys a lot of information very succinctly. It
tells you what the cement contains, and in roughly what proportions; it also
indicates the early and the 28-day strengths based on the standard mortar prism
test.
Sulfate-resisting Portland cement
You might have noticed a significant omission in CEM I there is no sulfate-
resisting Portland cement. Progress on a European standard for sulfate-resisting
Portland cement has been slow and, in the UK, for example, SRPC is still covered
by residual British Standard BS 4027 although this is largely academic since
SRPC is no longer manufactured in the UK.
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Standard Specifications for Portland Cement
Where sulfate resistance is required, in most concrete used in Europe now it is
achieved by using mixes containing Portland cement and mineral additions such
as slag or fly ash to achieve satisfactory sulfate resistance.
Some other cement-related European standards
Cements with a very low heat of hydration are specified as Special and are
included in EN 14216; these have a characteristic heat of hydration of not more
than 220 J/g.
BS EN 14216:2004 Cement: composition, specifications and conformity
criteria for very low heat special cements
Also:
BS EN 197-4:2004 Composition, specifications and conformity criteria for low
early strength blastfurnace cements
The standard for the testing of cement is EN 196-series: methods of testing
cement. There are ten of these but one is missing:
EN 196-1: 2005 Methods of testing cement. Determination of strength
EN 196-2: 2005 Methods of testing cement. Chemical analysis of cement
EN 196-3: 2005 Methods of testing cement. Determination of setting time
and soundness
There is no Number Four!
1
EN 196-5: 2005 Methods of testing cement. Pozzolanicity test for
pozzolanic cements
EN 196-6: 1992 Methods of testing cement. Determination of fineness
EN 196-7: 2007 Methods of testing cement. Methods of taking and
preparing samples of cement
EN 196-8: 2003 Methods of testing cement. Heat of hydration. Solution
method
EN 196-9: 2003 Methods of testing cement. Heat of hydration. Semi-
adiabatic method
EN 196-10: 2006 Methods of testing cement. Determination of the water
soluble chromium (VI) content of cement
1
EN 196-4 is absent because of practical difficulties in distinguishing some constituents chemically in
cement, such as microsilica. A draft text for Part 4 is in Technical Report CEN/TR 196-4: 2007
Methods of testing cement - quantitative determination of constituents. This gives a useful guide to
techniques.
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Standard Specifications for Portland Cement
10.3 Other specified cement properties
Both the ASTM C150 and EN 197-1 standards specify other physical and chemical
properties, including: composition, loss on ignition, insoluble residue, setting
times, limits on minor oxides (EN 197-1: SO3, clinker MgO, Cl); (C 150: SO3,
MgO) and limits on expansion using prescribed tests.
10.4 Dont ever mix the standards!
The distinctions between different Portland cement types made by ASTM C150-7
have no parallel in EN 197-1, where all Portland cement is CEM I. The majority of
CEM I cement will be, roughly speaking, similar to ASTM Type I or II cements,
but that this is not to say that they are necessarily equivalent.
While the compositional criteria for Portland cements under EN-197 and C 150
Portland cements may be broadly similar, they are not identical and the testing
procedures are quite different. For example:
# The upper limit for loss on ignition for CEM I cements under EN-197 is
5%; under ASTM C 150-07 it is 3.0% for all types except Type IV, where
the limit is 2.5%.
# The upper limit for Insoluble Residue under EN-197 for CEM I is 5%;
under ASTM C 150-07 it is 0.75% for all cement types.
# EN-197 uses mortar prisms to evaluate strengths while C 150 specifies a
mortar cube test; the mortar compositions are different and the strength
data from these different tests are not interchangeable.
If you were just laying a base for your garden shed, you might not worry too
much about the details of the specification process. However, suppose you were
an engineer on a major construction project who authorised the use of a cement
other than that specified. Faced with newspaper headlines like:
Hundreds crushed as new hotel collapses-wrong cement used
you would not be starting from a strong position in trying to argue that the
cement had not contributed to the problem, whether or not it actually had. So,
dont mix the standards.
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Standard Specifications for Portland Cement
Further reading, Chapter 10
The most useful further reading would clearly be to obtain copies of the
standard(s) most relevant to your location. Note that all standards are copyright.
C 150-07
ASTM Standard C 150-07, 2007, "Standard Specification for Portland Cement,"
ASTM International, West Conshohocken, PA. Available for download from:
www.astm.org
Price $37.00.
EN 197-1
BS EN 197-1:2000 Cement. Composition, specifications and conformity criteria
for common cements. Available for download from the British Standards
Institute shop at:
www.bsigroup.com/en/
Price 168.00 (UK Pounds).
(No, that isnt a typo EN 197-1 will cost you 168, or very roughly $275 US at
the exchange rate at the time of writing. However, you do get 52 pages,
compared with 8 pages for ASTM C 150-07, and EN 197-1 covers a wide range of
cements not just Portland cement.)
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11Cement concepts
So far we have looked at many individual components of cement and concrete.
Each one of these is necessary; now we can bring them all together to form a
more complete picture. What follows is partly revision, but we will look at cement
from a different perspective and apply what we covered in the previous chapters.
In the first part of this chapter, we are going to look at the two principal ways
that cements for different applications can be produced:
# Modify the Portland cement clinker
# Combine Portland cement with other materials, eg: slag, fly ash
In the second part of this chapter, we dig deeper. The aim is to develop an
intuitive understanding, a minds eye image in order to visualise both clinker
and hydrating systems.
11.1 Altering the properties of cement
First, lets look at two different approaches to producing cements that have
different characteristics, then in the next section we can practise visualising them
using our minds eye image.
The requirements of cement differ depending how concrete (or mortar) made
from it is to be used. For example, pre-cast products usually need a cement that
gives high early strength so that the concrete can be de-moulded and the moulds
re-used. Large pours of concrete need a cement with low heat of hydration to
minimise thermal cracking. Where sulfate is present in groundwater, the concrete
needs to be resistant to deterioration through sulfate attack.
These different demands need different cements with which to make the
concrete.
The characteristics of Portland cement can be altered in two principal ways. The
Cement concepts
first is to modify the cement clinker to produce the desired characteristics and
the second is to mix Portland cement with other materials such as slag or fly ash.
The first approach is exemplified in the American ASTM C 150 standard
specification, which describes five different types of Portland cements, neglecting
a further three air-entrained sub-types. ASTM C 150, particularly Table 1, is an
elegant and concise summary of how to control the properties of Portland cement
by varying its composition.
The second approach can be seen in the European EN-197 standard specification,
which describes only one Portland cement, CEM I, and a long list of other
cements containing mixtures of Portland cement and other materials.
Of course, blended cements are available in the USA, and some concrete in
Europe is still made with CEM I only, although the proportion has been
decreasing for some years. In the UK, CEM I is still available in bulk, but in
bagged form it is scarce, except for white cement. Typically, a bag of cement at a
builders merchant is CEM II/A-LL, a Portland-limestone cement, or CEM II/B-V, a
Portland-fly ash cement.
11.1.1 Altering the properties of cement: modify the Portland
cement
High early strength:
Suppose you wanted to make a high early strength Portland cement. You would
want to produce a clinker that had a high alite content and a low belite content,
since alite is more reactive than belite. You might also want to increase the alkali
content, as this will increase the alkalinity of the cement pore fluid and accelerate
hydration; of course, this might lead to problems with alkali-silica reaction if
reactive aggregates are present in the concrete, but here we are just talking
about principles.
You would also grind the cement finer as smaller particles will react more quickly.
You might also produce a mineralised cement; alite in mineralised cement is
more reactive than alite in normal Portland cement.
Of the above approaches, the two most commonly used are finer grinding of the
cement and increasing the alite content.
In ASTM C150-7, there are no particular limits on C3S and C2S contents for Type
III cement but the limits for fineness applicable to other cements are removed,
and minimum one-day compressive strengths are specified together with higher
minimum compressive strengths at 3 days than for other cements.
In EN 197, the specification for high early strength CEM I is similarly empirical
the cement has to meet the required strengths at 2 days and 28 days for that
strength class.
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Cement concepts
Low heat of hydration:
If you wanted to make a cement that had a low heat of hydration, you would
want to limit the proportions of the most reactive clinker minerals, the alite and
aluminate. The cement would then have a substantial belite content.
To illustrate this, the ASTM C 150-7 standard specification prescribes limits for
the clinker phases in cements of low or moderate heat of hydration:
# For a Type II cement (moderate sulfate resistance or moderate heat of
hydration) the specified maximum C3A content is 8% and the sum
(C3S+4.75C3A) must be 100 or less. (Note the weighting applied to the
C3A; this is because it is highly reactive, generating heat quickly, and
because limiting the C3A content reduces the potential for sulfate attack).
# For a Type IV cement (low heat of hydration), the maximum C3S content
is limited to 35% and there should be at least 40% C2S. Also, the
maximum permitted C3A content is 7%.
(NB: phase proportions here are calculated using the prescribed Bogue-type
formula; these limits do not apply in C 150-07 if optional heat of hydration limits
are to be applied).
Sulfate-resisting:
To make a sulfate-resisting Portland cement, the main consideration would be to
minimise the C3A content by making a clinker with a low Alumina Ratio; normally,
this would be achieved by adding an iron-rich component to the raw feed.
Instead of producing C3A, most of the aluminium will be then present in the
ferrite phase, which will have a higher ratio of iron to aluminium compared with
the ferrite in normal Portland cements. The objective in minimising the aluminate
content is obviously to limit the potential for the formation of ettringite in sulfate-
rich environments.
In ASTM C 150-7, the cement C3A content is limited to a maximum of 5%;
Annex A1 provides a modified calculation for the ferrite phase content if the
cement AR is less than 0.64, on the basis that such cements will not contain any
C3A.
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Cement concepts
11.1.2 Altering the properties of cement: combine Portland
cement with other materials
Weve just seen that one way of varying cement properties is to adjust the
composition of the Portland cement clinker. Another way is to blend Portland
cement with other cementitious materials, just as the Romans did when they
blended lime mixed with volcanic glass or ground brick and tile to produce
pozzolanic cements.
In the terminology of the European cement standard EN-197, mixtures of
Portland cement with other cementitous mineral additions are called Portland
composite cements if they are produced at the cement plant by intergrinding or
blending
1
. If mixed by blending at the concrete batching plant, they are
combination cements. In American usage, mixtures of Portland cement with
other cementitious materials are widely known as blended cements whether
blended or interground.
Here, we will use composite cements to mean blended cements with at least
two cementitious components, regardless of how or where they were blended.
Taking the three headings as before for variants of Portland cements:
High early strength:
To make a high early strength cement, the simplest approach to achieve the
highest early strengths would be not to blend anything with Portland cement;
most materials you might add, such as slag or fly ash, react more slowly than
Portland cement. However, microsilica and metakaolin are highly reactive and
may improve early strengths. Sprayed concrete mixes may contain metakaolin or
microsilica. Mixes of Portland cement and CAC can give early strength due to
flash setting.
Composite cements may be designated an R suffix under EN-197, indicating
high early strength, but in this context, high early strength is a relative
concept. Composite cements with the R suffix are almost always in the 32,5 or
42,5 strength classes and only have to achieve 10 MPa or 20 MPa
respectively at
2 days. For the highest strength class, 52,5, a cement has to achieve 30 MPa
at 2
days; 52,5 R cements are almost all CEM I (ie: pure Portland cements) ground to
increased fineness and often with raised alite contents.
1
Intergrinding means that the additional material (eg: slag or fly ash) is added to the clinker in the
cement mill. Blending means that the materials are mixed in some other way, usually using
specialised dry-blending equipment.
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Cement concepts
Low heat of hydration:
Combining other cementitious materials with Portland cement is an ideal way to
produce a cement with low heat of hydration. Composite cements containing
Portland cement with additions such as fly ash or slag will have a lower heat of
hydration because of the slower rate of reaction of slag and fly ash.
In EN-197 terminology, an example of a low heat cement would be a cement
containing a high proportion of blastfurnace slag: a cement labelled CEM III B
32.5N-LH would contain 66%-80% slag and 20%-34% clinker. The LH suffix
indicates a low heat cement. In EN-197, low heat is defined as a cement with a
characteristic heat of hydration of not more than 270 J/g.
Sulfate-resisting:
Composite cements made with Portland cement and either fly ash or slag can
give at least equivalent sulfate resistance characteristics to that obtained when
using sulfate-resisting Portland cement.
Suitably-designed mixes containing a Portland fly ash cement with, for example,
70% Portland cement and 30% fly ash should have good sulfate-resisting
qualities. Alternatively, a Portland blastfurnace cement could be used with a high
slag content, for example 30% Portland cement and 70% slag.
To give an example of a sulfate-resisting composite cement in terms of the EN
197-1 standard is not possible, since EN 197-1 does not currently cover sulfate-
resisting cements.
However, a cement labelled: CEM II/B-V 32,5R would have a fly ash content of
26% 35% and such cements are sold as having equivalent sulfate resistance to
that of sulfate-resisting Portland cement, if the cement has been shown to meet
additional criteria relating specifically to sulfate resistance. These additional
criteria are not specified in any European standard but in individual national
standards and the cement is labelled with an additional suffix, eg: +SR.
However, these bureaucratic niceties are not what we are focussing on here; the
main point is that composite cements containing slag or fly ash can offer
equivalent, or even better, performance for sulfate-resistance compared with
sulfate-resisting Portland cement.
Other benefits revisited:
The headings above dont really do justice to the positive characteristics of
composite cements, so, by way of revision, here are some more (see Chapter 7
for more detail):
Depending on composition, in addition to reduced heat of hydration and better
sulfate resistance, benefits of composite cements also include: possibly increased
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Cement concepts
later strengths; lower permeability and better durability; reduced efflorescence;
reduced shrinkage and creep; reduction in risk of ASR; reduced CO2 emission per
unit volume of cement; reduced consumption of natural resources. In the
interests of balance, we should also say that composite cements are more prone
to carbonation and might want more care with curing.
11.2 A minds eye image of cement
Call it a minds eye image, a conceptual model, or whatever you want;
anything we do is a little easier if we have some idea of the processes involved
and how they work.
If you drive a car, it helps if you know what the gearbox and clutch do in order to
drive it well. You dont have to be able to strip down the engine, but you do need
to have some minds eye image of each of the main parts of the car informing
you what they do and, roughly, how they work in relation to the car controls.
Have you tried to teach an aged relative how to use a computer? They might be
an absolute whizz, of course, but quite often older people have difficulties with
computers because they lack an understanding of them at a conceptual level. You
cant use Microsoft Word by trying to memorise a series of instructions; rote
learning for computers, or other complex systems, just doesnt work.
Similarly, rote learning isnt much good with cement. Most people interested in
cement are interested because they make it or they use it or they are
researching it; whatever your interest or level of understanding, it helps to have
a conceptual model of cement appropriate to the situation.
The model can be simple or complex, depending on what is most useful. A simple
model might be:
Cement is grey powder you use to make concrete that gives you nasty burns if
you get it on your skin.
This is a very useful and practical model that even the most distinguished
professor researching cement should have uppermost in his mind when
concreting his driveway. (If he does concrete his driveway, that is.)
However, having come as far as this, we might perhaps try to come up with
something a bit more illuminating. You should have the essential components of
a better model now, from the previous chapters. All you need to do is to practise
using your minds eye image.
Ive been using scanning electron microscopy and optical microscopy to examine
cement and concrete since 1981, during which time I must have looked at
thousands of samples of clinker, cement and concrete. My experience of
cementitious materials is therefore primarily visual and so Ive developed very
simple visual models of clinker, cement and concrete, based on standard
images. I use these models automatically, not just when examining material
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microscopically, but whenever Im thinking about cement, or someone is
describing to me a cement-related problem.
I call them models - you could just as well call them techniques or methods. The
point is that they are structured ways of conceptualising cementitious material,
be they clinker or concrete or anything else. They help to understand how
cement made from a particular clinker might behave, and they help to
understand the hydration products that are likely to form from a Portland
cement, or from a composite cement.
By adopting a structured approach to thinking about cement, you can break
down complex problems that appear hopelessly confused at first sight into
manageable pieces you can make sense of more easily. So, while these models
are simple, they are powerful, and therefore very useful. As with all models, they
represent only an approximation to reality; they are each a work in progress
that contains simplifying assumptions. If you wish, you can improve or otherwise
alter them and make them as complicated as you like.
There is one model for clinker and one for hydrating cement. Depending whether
you are a producer of cement or a user, one may be of more general use for you
than the other, but either way, have a go at using both.
Clinker composition: get a minds eye view of Portland cement clinker and
how differences in composition affect cement properties.
Cement hydration: get a minds eye view of the hydration process.
For each of these, there are two basic components:
# A concept of a reference material, either clinker or hydrated cement; this
is your archetype.
# A structured, logical, approach to working out how the reference material
would change if you changed the inputs.
An archetype is an original model on which something is patterned, (definition
from Nisus Thesaurus).
Inputs here means clinker or cement composition or cement type, or time or
temperature or some other factor.
In other words, you use your minds eye image to view an archetype
that you understand, and then you alter it by gradually adding in new
conditions.
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By changing the inputs, you can adjust the archetype in your mind using
thought experiments to allow for changes in compositions or other
circumstances so that your model is flexible and applicable to a wide range of
materials and situations.
Thought experiments are experiments you dont actually do, of course; instead
you explore ideas. Some thought experiments, like Schrodingers Cat, cant be
done in practice at all; those described here are far less obscure and could be
done in practice, but thought experiments do save a lot of time.
If you can use your minds eye image to work through each of the thought
experiments in the following two sections, you will have working conceptual
models that you can apply to cement clinker and to hydrating systems. You
might develop the models further over the years by refining them or adding new
pieces, and that would be very valuable, but the basic models, as described here,
should serve most people well for a long time.
Some of these thought experiments are easier than others. If you find any of
them difficult, dont worry. Come back to them again later and they should all
make sense eventually.
11.3 Cement clinker
If you are involved in cement manufacturing, this section is important because it
focuses on ideas that are fundamental to the chemistry of Portland cement
production. If you dont make cement but you use it or have some other interest
in it, this section is still important to you because it illustrates some of the basic
reasons why cement properties may change. If the cement you had delivered on
Thursday seems to be behaving differently from the cement you received on
Monday, the key parameters discussed here would be a good place to start
looking for the cause.
The starting point of these thought experiments is an image of the minerals in a
Portland cement clinker as seen in polished section, see Figures 11.1 and 11.2
below. Get this image fixed in your mind; this is your clinker archetype, the
starting point for your minds eye view.
Focus on it, remember it, visualise it and get to know it so you can recognise the
clinker minerals. Once it is firmly fixed in your mind, you can start to play with it
and adjust it using thought experiments based on the clinker compositional
parameters for Lime Saturation Factor, Silica Ratio and Alumina Ratio.
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Figure 11.1 Clinker archetype, SEM image
of polished section. Key: a-alite; b-belite;
c-aluminate (C3A); f-ferrite. Black areas
are pores filled with epoxy resin.
Figure 11.2 Clinker archetype, same image
as in Figure 11.1 but without the distraction
of the labels.
Whats special about this clinker? you may ask. Well, the point about this
clinker is that there is nothing special about it. It is just a normal, well-produced
clinker although perhaps a little slow-cooled. It is a typical clinker and we'll
assume it could equally well be used to produce cement compliant with either
ASTM C 150 Type I, or EN-197 CEM I.
Look at the individual crystals of clinker minerals. Identify the alite crystals. Now
look at the belite, the aluminate and the ferrite. Figures 11.1 and 11.2 both show
our standard image; Figure 11.2 is the same image without the labels showing
examples of the four main clinker minerals. You dont want your standard clinker
image to be cluttered with labels - just use the image to get to know what each
of the clinker minerals looks like, then focus on the image without the labels.
To help with adjusting this archetypal image in your minds eye in the thought
experiments that follow, the clinker compositional parameters for Lime Saturation
Factor, Silica Ratio and Alumina Ratio, are shown below for convenience. These
formulae govern the proportions of the clinker minerals and are a big help in
visualising the clinker as its composition changes.
Lime Saturation Factor: LSF=CaO/(2.8SiO2+1.2Al2O3+0.65Fe2O3)
Controls the proportion of calcium silicates present as alite - a higher LSF means
more alite, assuming the clinker is well-burnt with no additional free lime.
(There are other variations of this formula - use one of those if you are more
familiar with it.)
Silica Ratio: SR=SiO2/(Al2O3+Fe2O3)
Controls the proportion of silicate minerals in the clinker, ie: proportion of
(alite+belite).
Alumina Ratio: AR=Al2O3/Fe2O3
Controls the ratio of aluminate to ferrite phases.
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Clinker: thought experiment 1, changing the LSF
Suppose that this image is typical of the clinker produced by a cement plant on a
particular day and that the Lime Saturation Factor (LSF) is 94%, the Silica Ratio
(SR) is 2.5 and the Alumina Ratio (AR) is 1.6. The exact numbers dont matter
too much, we are just going to look at what happens as we change them.
Imagine you alter the raw materials going into the kiln by increasing the
proportion of limestone (assume it is pure calcium carbonate).
The clinker CaO content will increase, and so the LSF will also clearly increase;
the other oxides will decrease. The SR and AR will remain the same.
What effect does this have on your archetypal clinker image?
As you mentally add CaO, the proportion of alite in your standard clinker image
should increase and the proportion of belite should decrease. When you reach an
LSF of 100% there is very little belite, just a mass of alite, and the ferrite and
aluminate phases. This clinker will be harder to burn than the clinker in the
standard clinker image, but cement made from it might have slightly higher early
strengths, so long as the clinker wasnt overburned and all other things were
equal (particularly cement fineness, particle size). The heat of hydration will be
higher because of the increased proportion of alite.
Now imagine increase the LSF to something a little over 100% and visualise free
lime crystals forming - see Figure 3.13 for a picture of free lime in clinker. (Of
course, remember that in reality a little free lime will always occur below an LSF
of 100% due to clinker heterogeneities, especially coarse particles of limestone or
silica in the feed, or if the clinker is underburned, but dont worry about that
now).
Now picture the LSF slowly decreasing from over 100% to about 90%; first,
imagine the free lime disappearing and then the proportion of alite diminishing
and the proportion of belite increasing. This clinker will be much easier to burn,
but cement made from it will have lower early strengths than cement made from
the standard clinker (again, all other things being equal). Later strengths should
largely catch up, though it might take a year or so. The cement will have a lower
heat of hydration.
Clinker: thought experiment 2, changing the SR
Now imagine you increase the Silica Ratio from 2.5 to 2.7 by increasing the
proportion of silica in the raw feed. As the SR increases, the LSF decreases and
the AR stays the same.
What effect does this have on your archetypal clinker image?
The SR governs the proportion of total silicates - alite plus belite, so visualise the
alite and belite increasing and the aluminate plus ferrite decreasing. The AR
remains the same, so the relative proportions of aluminate and ferrite stay the
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same, however, the LSF is reduced, so picture a litle more belite and less alite.
The increased SR means that there will be less liquid, making the clinker harder
to burn; at the same time, though, the LSF is lower, making it easier to burn so
these effects will tend to cancel each other. Overall the clinker burnability may be
broadly similar to our standard clinker. All other things being equal, cement made
from this clinker would have lower early strengths than cement made from the
standard clinker because it contains less alite. However, the later strengths
should be at least as good and possibly better as the total silicate content is
slightly higher.
Now think of reducing the silica in the raw feed and the SR decreasing from 2.7
back through 2.5 down to 2.4. The LSF increases to about 100% and the AR
stays the same. Alite increases markedly and belite becomes scarce, as there is
now sufficient lime to form alite from all the available silica.
There is a little more ferrite and aluminate, in the same ratio as previously, and
fractionally less calcium silicates in total. All other things being equal, cement
made from this clinker would have higher early strengths than cement made
from the standard clinker because it contains more alite. The later strengths may
be fractionally lower as the total calcium silicate content is lower, although the
difference will be small.
Clinker: thought experiment 3, changing the AR
Now imagine increasing the Alumina Ratio to 2.0. You could do this by increasing
the Al2O3 content or by decreasing the Fe2O3. For this thought experiment, just
add some alumina and decrease the SiO2, CaO and Fe2O3 proportionally, don't
think about what raw materials you change to do this it might get complicated.
The LSF and SR will both decrease.
What effect does this have on your archetypal clinker image?
A lower LSF means less alite and a lower SR means less silicates in total and
more flux phases; a higher AR means the proportion of aluminate to ferrite will
increase. Visualise the alite proportion decreasing and the belite proportion
increasing; imagine also the total of aluminate and ferrite increasing. Because
there is more alumina and slightly less iron, there will be more aluminate phase
and less ferrite, so picture an increasing ratio of aluminate to ferrite.
The increased AR will make this clinker harder to burn (maximum liquid at the
lowest temperature is at an approximate AR of 1.38) but this will be offset by the
lower LSF and SR, both of which will make it easier to burn. Which effect would
win out is unclear, so lets suppose burnability will be similar to the standard
clinker. Cement made from this clinker will have a lower alite content and lower
silicates in total, so early and later strengths would probably be lower compared
with the cement made from the reference clinker (again, all other things being
equal). Although there will be less alite, there will be more aluminate and, since
aluminate is the most reactive of the four main clinker minerals, the heat of
hydration is likely to be higher compared with cement made from the reference
clinker.
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Starting with the standard clinker, try thinking of decreasing the AR to 1.4 but
this time by adding iron oxide. LSF and SR will decrease, so the total silicates will
decrease and there will be proportionally less alite and more belite.
Compared with the standard clinker, this clinker will be easier to burn as there
will be maximum liquid at minimum temperature and the SR will be lower, so
there will be more liquid overall. Also, the LSF will be lower, making combination
easier.
There will be less alite and less aluminate, so the heat of hydration will be lower.
Early strengths of cement made from this clinker will be a little lower; later
strengths may also be a bit lower as the total proportion of silicates will be less
and so there will be less hydraulic material present in the cement.
Note that if you lowered the AR by reducing the Al2O3 content, the SR and LSF
would increase.
Clinker: thought experiment 4, changing the free lime
Our archetypal image in Figure 11.1 doesnt show any free lime, although there
was some elsewhere in the nodule, say about 1.5% in the clinker overall.
Suppose we alter the burning conditions, while keeping the kiln feed composition
constant.
Suppose we initially had 56% alite and 18% belite (using the Bogue calculation),
and then we burned the clinker harder. The free lime content will decrease and
we will have more alite and less belite.
If that gave us 0.5% free lime instead of the original 1.5%, we might expect to
have around 60% alite and 15% belite. More alite is good, so we would have
better cement strengths, wouldnt we?
Well, no, probably not.
Yes, in principle, we want to make alite. However, there comes a point where
trying to get every bit of alite that you can becomes counter-productive. As we
said in Chapter 3, overburning produces less-reactive alite.
Suppose we now burn less hard and the free lime rises from 0.5% to maybe
2.5% or 3%. The alite should become more reactive and give better cement
strengths but there will be less of it; at some point, the optimum trade-off
between alite content and alite reactivity will be passed and cement strengths will
start to decrease again. If we allowed the free lime to rise further, we would
eventually start to have problems with expansion due to the hydration of free
lime within hardened concrete or mortar.
Where that optimum free lime content lies is likely to depend on a range of
factors, including the clinker LSF, feed combinability and the related issue of raw
material fineness (especially fineness of silica particles).
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Based on UK experience, a free lime of much less than 1% is likely to indicate an
overburned clinker. At least one manufacturer is happy to have 3% free lime in a
clinker of 100% LSF.
The optimum may also depend on how the cement is to be used. In a composite
cement, the presence of free lime, when hydrated, provides a ready source of
immediately-available CH to produce additional C-S-H or other hydration
products as the slag or fly ash, or other mineral addition, reacts. Of course, the
bulk of the CH will still be provided by alite hydration and the clinker LSF will
have a stronger effect in determining the available CH. The practical effects of
clinker LSF and free lime variability on paste microstructure in composite
cements are unclear and could make an interesting research project.
Softer burning has other benefits as well, saving fuel and prolonging the life of
the kiln lining.
A few general points
In all of the above, the mantra should be:
all other things being equal.
A second mantra should be:
with cement, all other things are never equal,
but, as these are thought experiments, it is OK to pretend.
If the visualised images get a bit hazy and you arent quite sure what should be
happening, go back and look at Chapter 5 on clinker, especially the plots of
combinability curves (Figures 5.1-5.5). All should become clear.
One main reason why all things might not be equal in the real world is that raw
materials are not pure oxides; it is difficult to add just one oxide, as most raw
materials contain more than one, and this would cause unintended secondary
effects. For example, if you added clay or fly ash to raise the Alumina Ratio, you
would also be adding more silica.
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Your freedom to compensate for this would depend what other raw materials you
were using; if you were also using milled silica sand, you could reduce the
proportion of sand to compensate for the additional silica in the fly ash. Even
then, other minor oxides in the fly ash may also have an effect; if the fly ash
contained magnesium, the temperature at which the melt formed on heating
might change. However, practical difficulties like this can be ignored in thought
experiments if appropriate - that is one of their great advantages. If you later
wanted to do one of the experiments for real, you would first identify these
secondary effects and apply the conceptual model to them also to predict the
results.
In other words, think what you want to achieve first, then work out how close
you can get to it in reality. Thought experiments can help with both.
Finally, if you have a cement made on Thursday that seems different from
cement made on Monday, but seems similar in compositional terms, the chapter
on cement variability looks at other reasons why this could happen.
11.4 Hydrated cement
11.4.1 Some useful principles
Everything to do with cement leads eventually to what happens when we add
water, whether in concrete, mortar, grout or some other cementitious material;
having an understanding of what happens as cement hydrates is therefore our
ultimate objective.
With clinker, the formulae for LSF, SR and AR help to visualise how clinker will
change as its composition changes. Unfortunately, as yet we have no such helpful
formulae for hydrating systems, so we adopt as our archetype the process of
hydration of the simplest hydrated Portland cement system, containing clinker
and interground gypsum only.
From this, using thought experiments, we can consider how changes in
water/cement ratio, or additions of fine limestone, slag, fly ash or microsilica, or
anything else we might care to add, are likely to affect the hydration products
that form. Factor in the paste porosity and permeability as well and we can get
an idea of how strong concrete made from that cement might be and how
resistant to deleterious processes.
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Seven useful principles:
1. Alite hydration produces calcium silicate hydrate (C-S-H) plus calcium
hydroxide (CH); belite hydration produces C-S-H, and maybe a little CH.
2. Aluminate and ferrite hydration release alumina (also lime and a little
iron); the alumina is of prime importance as it is required to form
ettringite and AFm phases.
3. The ratio of available alumina to sulfate in the cement paste controls the
relative proportions of monosulfate (AFm) phase and ettringite, but see
also Principle 4.
4. Principle 3 is modified in the presence of other anions that can substitute
for sulfate in AFm phase. In particular, carbonate from fine limestone can
substitute for sulfate in AFm to form hemicarbonate and then
monocarbonate; the displaced sulfate forming ettringite.
5. Fine filler effect: finely-divided inert material in cement acts as nucleation
sites at which dissolved material can precipitate to form hydration
products. An increase in the number of nucleation sites results in faster
dissolution and re-precipitation, allowing the cement to hydrate more
quickly. This results in more rapid strength growth at early ages. It also
seems to improve later strengths, probably by helping to produce a more
uniform microstructure.
6. The presence of additional available silica, due to the reaction of
pozzolanic or latently hydraulic additions to the cement, will enable
calcium hydroxide to react with the silica to form more C-S-H than would
be produced by Portland cement alone. C-S-H is the principal strength-
giving hydration product, so more C-S-H should mean higher strengths.
7. The ratio of calcium to silicon in C-S-H varies a little with calcium
availability in the hydration products. If more calcium is available, the
proportion of calcium hydroxide will increase. So, roughly speaking, if the
proportion of CH increases, the Ca/Si ratio in the C-S-H will increase.
Conversely, if there is less CH, the Ca/Si ratio in the C-S-H will decrease.
This liberates additional calcium from which more C-S-H can be produced.
Summary: if there is more CH in the paste, the C-S-H will have a higher
Ca/Si ratio and vice versa.
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It also helps to keep in mind the compositions of the reacting materials and of
the principal hydration products:
Alite: C3S (approximately)
Belite: C2S (approximately)
Aluminate: C3A (approximately)
Ferrite: C4AF (very approximately)
Free lime: C
Fly ash, fly ash , (low lime): mainly aluminosilicate glass
Slag: mainly calcium aluminosilicate glass (with more SiO2 and Al2O3 and less
CaO compared with Portland cement)
Calcium silicate hydrate: C-S-H, Si/Ca ratio approximately 0.5-0.6 in Portland
cement
Calcium hydroxide: CH
Ettringite: C3A.3CaSO4.32H2O
Monosulfate: C3A.CaSO4.12H2O
Monocarbonate: C3A.CaCO3.11H2O
Hydroxy-AFm: C4AH13
and
_
Hemicarbonate: C4AC0.5H12
+ Other minor phases
11.4.2 Hydration of different cements
To start with, think of a Portland cement that is composed only of ground clinker
and gypsum added at the cement mill. It has no interground limestone, or
grinding aid that affects cement hydration. It contains no carbonate and no
carbonate is allowed to penetrate from outside. (In Europe, this almost has to be
a thought experiment because most CEM I contains interground limestone,
unless you use white cement.) The image in Figure 11.3 below, reproduced from
Figure 6.3 for convenience, is a good archetype and we'll use it for the thought
experiments that follow.
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Figure 11.3 Archetypal image: polished
section of cement paste, age 2 years, made
using ordinary Portland cement, w/c=0.40.
Key: c - unhydrated cement; C-S-H - calcium
silicate hydrate; CH calcium hydroxide; p
pore; Circle A contains C-S-H, CH and is
assumed also to contain AFm and AFt phases.
CH is just visible, AFm and AFt are not visible
as they are too small.
In most of what follows, we will be thinking of the cement paste fraction of the
concrete (or mortar etc.). Concrete is not just cement paste with stones in it,
because the presence of aggregate introduces other important physical factors
such as the water demand of the aggregate and the interface between the
aggregate and the paste. However, we want to concentrate on the hydration
process and this is most simply done by thinking of pastes - just cement and
water.
You may first want to review the cement hydration process outlined in Chapter
6.3.4.
Thought experiment 5: effect of water/cement ratio
The next thought experiment is to visualise some cement pastes with different
water/cement ratios. It should be really easy, because there are some pictures
showing exactly this in Chapter 6; for convenience, here they are again (Figures
11.4-11.7).
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Figure 11.4 Polished section of cement paste,
age 2 years, made using ordinary Portland
cement, w/c=0.33.
Figure 11.5 Archetypal image: polished
section of cement paste, age 2 years, made
using ordinary Portland cement, w/c=0.40.
Figure 11.6 Polished section of cement paste,
age 2 years, made using ordinary Portland
cement, w/c=0.50.
Figure 11.7 Polished section of cement paste,
age 2 years, made using ordinary Portland
cement, w/c=0.60.
In this particular experiment, dont think about individual hydration products, just
concentrate on three components: the cement hydration products as a whole, the
pores and the remaining cement particles that have not hydrated. Implicitly,
there is also a fourth component, water, filling the pores.
Think firstly of mixing 1 kg cement with 400 g water to give a water/cement ratio
of 0.4, then curing the paste under water for a year or two, until it is mature and
little further hydration will occur.
Picture the hydrating cement: as time passes, the proportion of hydration
products increases, the proportion of unhydrated cement decreases and the
water-filled gaps are gradually replaced by hydration product.
In principle, according to the Powers-Brownyard model, at w/c=0.4, most or all
of all the cement should hydrate because we supplied additional curing water. In
practice, it wont, because of the formation of thick coatings of hydration product
around the unhydrated relicts of larger cement grains that restrict further access
to water.
By 28 days, perhaps about 80%-90% of the alite has hydrated, together with
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about half of the belite, almost all of the aluminate and perhaps half the ferrite.
Some of what remains unhydrated will probably never hydrate, although
hydration will continue at a slow, and ever slower, rate almost indefinitely. After a
year or two, hydration will have mostly ceased.
The archetypal image in Figure 11.3 (and in Figure 11.5) is our archetype; it
shows paste made with a water/cement ratio of 0.4 after 2 years. It is composed
largely of cement hydration products, with a little unhydrated calcium silicate
(top left) and some ferrite (bright, in larger relict cement grains). There are some
pores visible; these are capillary pores and would have been water-filled. In the
polished section, water in capillary pores has been replaced by epoxy resin.
To summarise, a mature Portland cement paste (w/c=0.4) contains hydration
product, some pores, some unhydrated cement, a little water or pore fluid and
maybe some entrapped air.
Next, visualise how a mature paste made with w/c=0.5 might appear. (Don't
cheat and look at the images, just think about it!) There will be more water and
less cement in the paste, so we would expect a higher porosity and fewer
remaining unhydrated cement grains.
Now have a look at Figure 11.6, which shows exactly this; the paste
microstructure is considerably more porous than the paste made with w/c=0.4 in
Figure 11.5. There is still some residual ferrite; some of this may have hydrated,
we can't really tell from the images, but what is there now will probably persist
almost indefinitely.
While thinking again of the paste made with w/c=0.4, now picture a mature
paste made with w/c=0.6. There will be much less cement and much more fluid-
filled pore space; the hydration products will be more porous, with larger
capillary pores; again, this is just what Figure 11.7 shows. There is a clear trend
in the characteristics of the images in terms of porosity and residual unhydrated
cement as we go from w/c=0.4 through w/c=0.5 to wc=0.6.
Finally, consider a paste made with w/c approximately 0.3. The trend continues
in the opposite direction; we would expect a lot of unhydrated cement and little
porosity. According to the Powers-Brownyard model, not all the cement can
hydrate because there is not enough volume to accommodate all of the hydration
product. That is apparent from Figure 11.4; very little porosity is visible but
unhydrated cement grains are numerous. By extension, since there is little
capillary porosity visible, the available water is also very limited. Assuming
hydration product to occupy 2.2 times the volume of the unhydrated cement, it is
clear that most of the remaining cement cannot hydrate; there is not enough
space for the hydration product, or sufficient available water.
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Thought experiment 6: changing the sulfate/alumina ratio
This expands Principle 3 above. Although they represent only a small proportion
of the total paste, ettringite and AFm phases are important; they affect concrete
setting properties and can have an effect on long-term durability.
The balance between available alumina and sulfate in the cement paste controls
the relative proportions of AFm phases and ettringite. In this thought experiment,
think of three cements, all made from the same clinker as used in our cement
archetype above, but containing different amounts of gypsum added when the
cement was milled.
Well call these low sulfate, medium sulfate and high sulfate mixes; the
actual numbers arent important here but think of them as, say, 1.5%, 3.0% and
4.5% SO3 if you like. The cements are used to make pastes, all at the same
water/cement ratio and cured until they are mature, say for a year or more.
Assume there is sufficient sulfate to prevent a flash set at the lower sulfate
contents and that any false-set that might occur is mixed through at the higher
sulfate contents. Dont worry about the exact numbers shown, they are only
intended to be illustrative, and just follow the arguments for each paste.
In a mature paste, what hydration products are present?
Medium sulfate mix: suppose the cement in the archetype mix above contained
a medium level of sulfate. In our mature paste, hydration has virtually
completed and the principal hydration product is C-S-H. Some CH is present, and
there is sufficient available sulfate to combine with all the available alumina to
form monosulfate phase. A small surplus of available sulfate produces a little
ettringite from some of the monosulfate. This is our reference paste to compare
with the following pastes as we change the amount of sulfate.
This paste contains: C-S-H; CH; AFm as monosulfate and a small amount of
ettringite.
Suppose there is less sulfate:
Low sulfate mix: in this paste, the available alumina is about the same as in the
medium sulfate mix; there is less available sulfate, all of which is present in AFm
phase as monosulfate, but there is still an excess of available alumina.
Consequently, there is no ettringite at all, because this requires a higher ratio of
sulfate to alumina. The small deficit of sulfate is accommodated by the formation
of hydroxy-AFm phase, in which sulfate is partly replaced by hydroxide.
This paste contains: C-S-H; CH; AFm as monosulfate and hydroxy-AFm; no
ettringite.
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Suppose there is more sulfate:
High sulfate mix: compared with our medium sulfate reference paste, this
paste with a higher sulfate content has more available sulfate and there is now
sufficient to convert almost all the available alumina to ettringite, with a little
residual monosulfate.
This paste contains: C-S-H; CH; ettringite; a little AFm as monosulfate.
At higher still levels of sulfate, all the available alumina will have formed
ettringite; there will be some residual gypsum as no other sulfate-containing
phases can form.
This experiment has considered what might be present in mature pastes because
it is easier to do this when the reactions have largely stopped. At early ages, the
reactions are more complicated and there will be much local variability. Cement
particle size and crystal microstructure, to name just two factors, affect the rate
at which reactants become available. Also, not all the sulfate in the cement is
ultimately present in ettringite or monosulfate; some is taken up by the C-S-H,
as is some alumina. The use of the term available is used to allow for these
uncertainties.
Thought experiment 7: add interground limestone
In recent years, an increasing proportion of Portland cement worldwide has
contained a small amount of interground limestone, typically up to 5%. The next
change to our archetype of a basic Portland cement should therefore be to add
some interground limestone. With closed-circuit cement milling, the particle size
range is less than with an open-circuit mill. There are fewer coarse particles and
a much smaller proportion of very fine particles; limestone is softer than clinker,
so intergrinding it with clinker in a closed-circuit mill will produce very fine
limestone particles (<1 !m) and these compensate for the lack of very fine
cement particles. These fine limestone particles will have both physical and
chemical effects.
Imagine mixing cement containing fine limestone with water. At the instant of
mixing, before the cement and water react, think of the fine limestone dispersed
between the coarser cement grains. The fine limestone occupies space that would
otherwise be occupied by water. The mix will be more cohesive, reducing
bleeding. The cement may also be ground coarser, giving better control over
early hydration, strength growth and heat evolution and will also save energy.
The first effects of limestone intergrinding are therefore physical and are in some
ways beneficial. The water demand might increase, depending on the particle size
of cement and limestone; this would reduce strength and so not be beneficial.
Imagine the fine particles of limestone being engulfed by C-S-H and ettringite
precipitating around them. This is Principle 5, the fine filler effect. The fine
limestone will act as nucleation sites for the formation of hydration products; this
will tend to reduce setting times and increase early strengths by increasing the
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rate at which the cement hydrates. As noted in Principle 5 above, it may also aid
later strengths.
How will the chemistry of the cement paste change?
Although limestone is widely used as aggregate, calcium carbonate is not inert in
cement pore fluid. The smaller the limestone particles are, the quicker they are
likely to react. Principle 4 says that this will affect the formation of ettringite and
monosulfate. Some of the interground limestone will dissolve, with the calcium
contributing to the formation of C-S-H and other hydration products and the
carbonate forming AFm phases.
Where monosulfate has formed, carbonate from the limestone displaces the
sulfate. The sulfate forms ettringite from existing monosulfate and the carbonate
forms AFm phase as hemicarbonate. Eventually, all the monosulfate disappears,
replaced by hemicarbonate and ettringite.
The hemicarbonate may then react with more carbonate, if available, to produce
monocarbonate. (Monocarbonate contains twice as much carbonate compared
with hemicarbonate, so hemicarbonate will tend to form if carbonate is scarce in
relation to the total amount of AFm phase, with monocarbonate forming as more
carbonate becomes available).
Under 0.5% carbonate by mass of cement is typically enough to prevent
monosulfate formation in cement paste; this is roughly 1% limestone. If 5%
limestone is present in the cement, there is a large excess of available carbonate
and the principal stable AFm phase where interground limestone is present is
therefore most likely to be monocarbonate.
In summary, cement containing interground limestone is likely to contain
ettringite, with monocarbonate tending to be the principal AFm phase instead of
monosulfate. This should have no adverse effect on the performance of the
cement; indeed it should be beneficial to strengths due to the fine filler effect and
to durability by a more effective blocking of capillary pores by the platelets of
monocarbonate AFm phase together with ettringite.
Intergrinding up to 5% fine limestone with the clinker is a relatively recent
development (how recent depends where you are). However, limestone has been
used as an aggregate since concrete was first used. If limestone is crushed for
use as aggregate, it will contain limestone dust, so the presence of fine limestone
in concrete is actually not all that new.
An accountants view of adding 5% limestone to cement might be that, since
limestone is cheaper than cement, the purchaser is getting a bad deal. In
practice, the performance of the cement should not be adversely affected and
may be enhanced. (EN 197-1 requires that a cement containing 5% mac - which
may be fine limestone - should meet the same performance criteria as if the mac
were not present.) There should also be a slight saving in the energy required to
produce the cement.
Thought experiment 8: add microsilica (silica fume)
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Microsilica is a by-product of the silicon industry consisting of small, rounded,
glass particles approximately 0.1 !m across. It is typically composed of 85% or
more silica, with some potassium, aluminium, iron, magnesium, calcium and
other impurities. It is highly pozzolanic with a large surface area.
Think of our archetypal Portland cement paste use the image in Figure 6.3,
reproduced yet again for convenience in Figure 11.8 below. Then imagine adding
to it a small amount of microsilica, say 3% by weight of cement, and mixing to a
paste with w/c=0.5. How will the microsilica affect the properties of the paste?
Figure 11.8 Polished section of cement paste,
age 2 years, made using ordinary Portland
cement, w/c=0.40. Key: c - unhydrated
cement; C-S-H - calcium silicate hydrate; CH
calcium hydroxide; p pore; Circle A contains
C-S-H, CH and is assumed also to contain AFm
and AFt phases. CH is just visible, AFm and AFt
are not visible as they are too small.
We have added very fine and reactive material composed largely of silica;
assuming the microsilica to be properly dispersed, the fineness should have the
physical effect of improving the cohesiveness of the paste. In concrete, this
should reduce bleeding.
How will the chemistry of the cement paste change?
Principles 5 and 6 will apply; think of the numerous small particles acting as
nucleation sites for the formation of hydration products. This should improve
early concrete strengths and probably also reduce setting times. As the
microsilica itself then starts to react, it will contribute silica to the cement
hydration products, forming additional C-S-H from the CH in the paste. Look
particularly at the CH in the paste without microsilica in Figure 11.8, and then
visualise the extent of CH in the paste diminishing as the C-S-H increases with
microsilica addition.
The Si/Ca ratio of the C-S-H will increase from approximately 0.5 to 0.6 or more.
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With increasing levels of cement replacement by microsilica, the quantity of CH
will decrease further and the Si/Ca ratio of the C-S-H will increase, releasing
more lime for C-S-H formation.
In summary, cement containing microsilica should have a dense paste structure
with an increased proportion of C-S-H and a decreased proportion of CH.
Strength should be enhanced and permeability decreased, leading to better
durability.
Assuming the microsilica to contain a negligible amount of alumina, the addition
of microsilica will not affect the ratio of sulfate to alumina and so the relative
proportions of monosulfate and ettringite shouldnt be altered.
Thought experiment 9: add granulated blastfurnace slag (gbs)
Blastfurnace slag is a by-product of iron smelting. When the molten slag is cooled
rapidly using water from about 1500 C to 800 C, it forms a granular, latent
hydraulic, material composed of about 95%, or more, glass. The three principal
oxides are those of calcium, silicon and aluminium. Compared with Portland
cement, slag used in concrete contains less CaO and more SiO2 and Al2O3. Slag is
not as reactive as Portland cement and ideally is ground finer.
The proportions of Portland cement and slag in a composite cement vary widely,
typically from 30% slag to 70% or more. Suppose we have a mix containing 50%
of our archetypal Portland cement and 50% ggbs at w/c=0.5.
When first mixed with water, the Portland cement fraction of the mix reacts more
quickly than the slag and so has a higher effective w/c ratio than if the mix were
100% Portland cement. The paste microstructure for the first few days or weeks
is therefore more porous compared with a 100% Portland cement mix. As the
slag hydrates, the porosity is reduced and eventually the paste should become
less porous compared with a 100% Portland cement mix.
The finest of the slag particles probably provide nucleation sites on which
hydration products form, especially if the slag has been ground finer than the
clinker
1
. Principle 4 will therefore apply to some extent. (If the Portland cement
also contained interground limestone, the limestone may act to accelerate both
cement and slag hydration; however, our archetypal Portland cement contains no
limestone so we wont consider this further).
The main effect of the slag is on the proportions of the hydration products and
their composition, and on the paste microstructure.
In our mix of Portland cement and slag, at an early age (eg: one day) the
Portland cement fraction has hydrated more than the slag component, and the
hydration products are broadly those of the Portland cement archetype.
Gradually, the slag reacts.
1
Slag is harder to grind than clinker, so intergrinding slag and clinker produces cement in which the
slag is coarser than the clinker. Preferably, the slag should be finer than the clinker, so ideally the two
are milled separately and then blended.
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How will the chemistry of the cement paste change?
Think of the composition of the slag; compared with Portland cement, the slag
has a higher ratio of Si/Ca and also of Al/Ca (compare the typical analyses in
Tables 3.2 and 7.1). The main effect on the hydrating system will be to increase
the ratio of total available Si/Ca compared with that from the Portland cement
alone and Principle 6 will apply. The proportion of CH in the paste will decrease,
the proportion of C-S-H will increase and the Si/Ca ratio of the C-S-H will
increase.
Principle 3 will also apply. The slag contributes more alumina than sulfate, so the
ratio of alumina to sulfate in the paste will increase. Any ettringite that had
formed earlier from Portland cement hydration will be lost and virtually all of the
available sulfate will be present in the form of monosulfate. Hydroxy-AFm will
form if insufficient sulfate is present to combine with the available alumina to
produce monosulfate.
Comparing the Portland cement paste in Figure 11.8 with the image in Figure
11.9 containing Portland cement and slag, there are two main differences visible
in the hydration products: in the paste containing slag, there is more C-S-H in
relation to CH, in fact, there is very little CH visible in Figure 11.9; most has been
converted to C-S-H.
The second difference is that, in Figure 11.8, there isn't any AFm phase visible.
Some will be present, but the crystals are too small and dispersed to be
apparent. In contrast, in Figure 11.9, platy crystals of AFm are clearly visible and
widespread. This is because alumina from slag hydration has produced additional
AFm. In the absence of any available carbonate, the AFm phases will probably be
a mixture of monosulfate and hydroxy-AFm.
Figure 11.9 Polished section of concrete
containing 50% Portland cement and 50%
ggbs, age approximately one year. Key: c-relict
Portland cement particle; s-residual
unhydrated slag; arrowed features-platy
crystals of AFm (mainly monosulfate) phase.
Note how the AFm crystals occupy pore space,
reducing porosity and permeability.
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In addition to acting as a physical barrier, monosulfate crystals can convert to
another AFm phase, Friedels salt, in the presence of ingressing chloride; to some
extent this may act to limit potential corrosion of steel reinforcement. The
presence of slag in composite cements can therefore be highly beneficial by
increasing both strength and durability. In addition, it makes use of a by-product
material and reduces the amount of Portland cement used, with savings in
energy, raw materials and carbon dioxide emissions. (The down side is that, as
mentioned previously, slag needs a more extended curing period than Portland
cement. Depletion of CH in the paste may result in a higher susceptibility to
carbonation and risk of reinforcement corrosion, the latter being partly offset by
a lower paste permeability).
Most sulfur in slag is present as sulfide, not as sulfate, although a small amount
of sulfate may be present. Sulfide released by slag hydration probably becomes
incorporated into AFm phase. Other minor hydrated phases will be present in
composite cements containing slag, in particular, a phase similar to hydrotalcite.
In summary, compared with a paste made using Portland cement alone, a paste
made from a composite cement containing slag would be expected to contain
more C-S-H, less CH, more monosulfate and less ettringite probably no
ettringite at all if there is sufficient slag. The increased proportion of C-S-H may
improve strength (depending on slag content, fineness and reactivity) and reduce
the paste permeability. The infilling of pore space by the platy monosulfate
crystals may add to strength and will certainly contribute to lowering permeability
(Figure 11.9).
If the Portland cement contained interground limestone; the limestone would
supply carbonate for the formation of AFm phases. Depending on the relative
proportions of available sulfate, alumina and carbonate, a mature paste or
concrete would contain C-S-H, a little CH; much AFm due to alumina from slag
hydration, and possibly ettringite. The AFm would be present as a mixture of
monosulfate and hemicarbonate, or hemicarbonate and monocarbonate, or all
monocarbonate.
Thought experiment 10: add low-lime fly ash
Fly ash is a pozzolanic by-product of electricity generation using coal. It is the
non-combustible fraction of the coal that melted and then solidified in flight,
forming near-perfect spheres. Low-lime fly ash is derived from minerals such as
quartz and feldspar and so the principal oxides are silica and alumina, with some
potash and soda. Residues of iron and sulfur from the coal will be present, and
some carbon. Composite cements containing Portland cement and fly ash
typically contain up to 30% fly ash, sometimes more.
Fly ash in a composite cement has two physical effects:
Think of the spherical shape of fly ash particles aiding concrete workability by
acting as small ball bearings in the mix. This means that lower water/cement
ratios may be used in mixes containing fly ash compared with mixes containing
only Portland cement, or Portland cement and other angular particles such as
slag.
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The finest fly ash particles are less than a micron across - imagine them also
contributing to some extent to providing nucleation sites for the formation of
hydration products (Principal 5).
How will the chemistry of the cement paste change?
If we consider the low-lime fly ash as principally an aluminosilicate glass, the
effects on the chemistry of the paste will be somewhat similar to those of slag.
Principles 3 and 6 will apply.
Our archetypal cement paste contains no limestone, so we don't need to consider
AFm phases containing carbonate. fly ash reaction releases silica, resulting in an
increased proportion of C-S-H and a decreased proportion of CH.
Fly ash reaction also releases alumina, altering the balance between available
sulfate and alumina. This results in an increase in the proportion of monosulfate
and, probably, the disappearance of any ettringite that had formed initially before
the fly ash reacted significantly. As with the slag mix above, hydroxy-AFm will
form if insufficient sulfate is present to combine with all the available alumina to
produce monosulfate.
Fly ash is less reactive than either Portland cement or slag and so early strengths
will be lower. However, later strengths will be enhanced by the formation of
additional C-S-H, reducing porosity and permeability. Strengths will also be
enhanced by the reduction in water requirement due to the lubricating action of
the fly ash spheres. Comparing the strengths of fly ash and Portland cement
mixes, the relative strengths will depend on curing temperature.
If the mixes are cured at ambient temperature (nominally 20