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Through the twentieth century considerable efforts were made to

understand the basic chemistry of cement. The work of Rankin and
Wright, Lerch and Bogue, Taylor, Nurse, Welch, Gutt and others led
to a model for cement manufacture and hydration which is still in
everyday use today throughout the World. However, with increasing
use of waste streams in cement production both as fuels and raw
materials, how do the resulting compositional variations affect our
product?

I began learning cement chemistry working as a microscopist at

Blue Circle's Research Department at Greenhithe in Kent in 1979.

My geological
background was invaluable as I started making laboratory mixes and
firing then to make new rocks which I then examined under the
microscope. In this way I learned about the observable differences
which small modifications to chemistry can make for the potential
quality of cement. Optimising the raw materials involves
understanding their relative grindabilities as well as
combinabilities in various combinations. The optimal mix will not be
the same in every market.

I can offer an assessment of the possibilities for raw materials to

make the desired clinker in the most economical manner. My
articles inInternational Cement Review offer an insight into the
methodology used.

In recent years the effects of cement manufacture on the

environment have been in the spotlight and the drive now is to
reduce CO2 emissions from both the process and the combustion as
well as reducing NOx and SO2. I have experience of the methods of
reducing environmental impact and also the workings of the
European carbon trading scheme.

The following relates to the basic chemistry involved and some of

the possible implications.

Background

The clinker chemistry model as commonly used starts with the

premise that the essential ingredients of cement clinker are the four
oxides; SiO2, Al2O3, Fe2O3 and CaO which, when heated to
approximately 1450C in the cement kiln, form the four compounds;
Ca3SiO5, Ca2SiO4, Ca3Al2O6 and Ca2AlFeO5. These are more generally
known, using the cement industry notation, as C3S, C2S, C3A and
C4AF, or else as alite, belite, aluminate and ferrite.

Using pure components and working under laboratory conditions,

the fundamentals of how cement clinker is formed were elaborated
and the ratios used today; Lime Saturation Factor (LSF), Silica Ratio
(SR) and Alumina to Iron ratio (AF); with their implications for
strength development, setting times and so on were established.

In practice of course it was always known that this was a

simplification of the actual chemical mix in cement clinker and the
compounds formed. The presence of the alkali oxides Na2O and K2O,
of sulphur dioxide SO3 and of MgO were recognised as having an
influence on the clinker formation process.
With increasing use of waste derived fuels and alternative raw
materials, the significance of the minor components in cement
clinker increases. Some traditional rules of thumb may need to be
modified in the light of the new situation.

Liquid Formation

As an example the optimum value for the AF ratio, which will

produce the maximum liquid at the lowest temperature, was
identified as 1.38, as seen in the graphic reproduced as

Fig.1.

Figure 1. Liquid Phase Formation and Liquid Composition

As the proportions of Al2O3 and Fe2O3 move away from the optimum
1.38, the quantity of liquid at the lower temperature decreases
relative to that at the higher temperature. The importance of more
liquid at lower temperature is that nodulisation and silicate
formation are both affected by the presence of significant quantities
of liquid, so the burnability of the feed and the efficiency of clinker
manufacture are directly affected.

In 1935, Lea and Parker suggested modifications to the calculation

for liquid quantity, assuming that any MgO content up to 2% is
present as liquid at 1338C or above and that all the Na 2O and K2O
present are dissolved in the liquid at these temperatures. In the
presence of appreciable quantities of SO3 this last assumption needs
to be modified, because the alkalis and sulphate form a separate
liquid, immiscible with the main clinker liquid.

In dry process and precalciner plants, the difference becomes of

considerable significance as the use of petroleum coke and other
sulphur-containing fuels combined with the recirculating loads of
SO3 and alkalis lead to enhanced liquid quantities entering the
burning zone. It is not unusual for clinker to contain 1% to 1.5%
SO3, all of which will be molten above about 850C. In a precalciner
kiln the recirculating load can be double this, so there may be 3%
SO3 as liquid combined with possibly half as much again alkali or
calcium oxide, giving an extra 4.5% liquid above that indicated in
Figure 1. In a situation where there is an AF ratio of 1.38, 2% MgO
and 1.5% clinker SO3 is it quite possible that the clinker may contain
well over 30% liquid well before the burning zone. In most instances
this will not be acceptable in terms of coating tendency and
potential ring formation within the kiln and a move away from the
traditional optimum alumina to iron ratio will be necessary to
optimise the kiln performance.

Other effects on the AF ratio and the burnability of the feed result
from the presence of steel in tyres used as fuel. Allowance must be
made for the presence of iron from the steel in calculating the feed
composition in relation to the desired clinker chemistry. It must also
be considered, however, that tyre ash will not be included in the kiln
during startup and on the occasions when the tyre supply must be
stopped for one reason or another without actually bringing about a
kiln stop. Unless it is possible to provide an additional iron rich
source to be included when tyres are not being burned, it will be
necessary to use an alumina to iron ratio which will tolerate changes
of the order which may occur.

Potential for Strength Development

Within the cement and concrete industry the potential quality of a

cement is usually judged in the first instance by the Lime Saturation
Factor or by the C3S content as determined using the Bogue
calculation. In simple terms the more C3S is present the better will
be the 28 day strength. The Bogue potential compound composition
can be calculated using a set of four simultaneous equations, each
one expressing the quantity of SiO2(S), Al2O3(A), Fe2O3(F) or CaO(C)
in each of the clinker compounds C3S, C2S, C3A and C4AF:

The solution to the equations will give the amount of S, A, F and C

in C3S, C2S etc and therefore, in the pure system, the quantities of
each compound.

In cement clinker, however, pure compounds are not formed. The

minor components in the raw feed or from the fuels also become
incorporated into the C3S, C2S, C3A and C4AF. The modified silicate
compounds C3S and C2S are known by the mineral names alite and
belite respectively. The compounds which are liquid in the kiln are
generally referred to as the aluminate phase and the ferrite phase or
simply aluminate and ferrite. Table 1 shows typical real compositions
of the clinker compounds, compared to the pure
compounds compositions.

Table 1. Comparison of Actual and Theoretical Compositions of

Clinker Compounds

As long ago as the late nineteenth century, much of the original

identification and characterisation of the clinker minerals was
carried out using optical microscopical techniques. The relative
quantities of the various visually distinct minerals were observed
and the effects of different concentrations of each on clinker quality
were noted. In an extension of the optical microscopic
examinations, the use of the scanning electron microscope with x-
ray microanalytical capability has allowed petrologists to obtain
accurate analyses of the individual clinker minerals without the need
for extensive extraction techniques. This procedure has allowed a
large number of results to be produced. The typical analyses shown
in Table 1 are averages of many such analyses from many sources.
SEM analyses and interpretations of clinker are routinely carried out
at WHD Microanalysis Consultants Ltd.
With a more accurate idea of the actual compositions of the clinker
minerals, it is possible to substitute the values for S, A F and C in

the pure
compounds with those of more typical compositions or, if a detailed
x-ray microanalysis of a particular clinker is available, with the
actual composition of the minerals in that clinker. Other techniques,
including quantitative x-ray diffraction analysis and microscopic
point counting are also available for assessing more accurately the
actual compound composition of clinkers as opposed to the potential
compound composition given by the Bogue calculation. Table 2
shows a comparison of the results from each of these methods on a
single clinker sample, compared to the Bogue calculation result.

Figure 2 Example of x-ray microanalysis of calcium silicate.

Bogue Potential Modified Quantitative Point

Compound Bogue XRD Counting
Composition Calculation

Alite 57.7 65.6 68.8 61

Belite 18.6 12.7 14.2 22

Aluminate 9.7 6 9.6

Ferrite 9.7 13.1 8.3 17

Free lime 0.7 0.7 nd 0.03

Table 2. Quantitative Compound Compositions Determined

in Various Ways on the Same Clinker

In every case the other methods give a higher value for the alite
content of the clinker than the Bogue potential compound
composition, due to the incorporation into alite of minor
components.

There are obvious implications in these results for quality control

and optimisation of the burning conditions in the kiln. The presence
of appreciably higher levels of alite in the clinker than anticipated
indicates that the effective LSF of the mix travelling through the
burning zone is higher than the base chemistry would
suggest. There is a strong link between the LSF of the kiln charge
and burnability, with higher LSF mixes proving more difficult to burn
(and therefore requiring more heat to achieve combination) than
lower LSF mixes. If the clinker contains a variety of elements which
are included in alite crystals but are not taken into account in the
LSF calculation, then the desired combination will be more difficult
to achieve. This may be manifested in difficulty reducing free limes
to the target levels, in excessive heat consumption and possibly in
increased emissions from the kiln. These will also be associated
with reduced output.

Minor Elements from Waste Streams

As well as directly affecting the ratios used in clinker manufacture,

the use of waste streams as alternative raw materials or fuels
frequently introduces elements which have not traditionally been
found in significant quantities in Portland Cement clinker. Many of
these have implications for emissions and compliance with the
appropriate environmental legislation. Some of them also have
implications for the cement chemistry and the ease of combination
of the clinker raw feed constituents.
Common examples of these elements would be phosphorous from
MBM used as kiln fuel, magnesium from blastfurnace slags used as
alternative raw materials and manganese from various waste
streams derived from steel manufacture. In 2005 Earl Smith of
Grace Construction provided an extensive list of possible minor
elements and compounds which might be introduced from waste
materials (ICR December 2005). A number of these elements are
regarded as problematic due to their ability to form stable
compounds or solid solutions with C2S, thereby preventing
combination in the kiln and leading to high free lime contents and
poor quality cement. This list would include strontium, boron and
phosphorous. Sulphate could also be included because at moderate
concentrations it has been reported as restricting or preventing the
formation of C3S. In September 2003 an article in ICR described the
influences of sulphate on C3S formation and also the rle of fluorine
in counteracting this. Mention was also made of the effect of
phosphorous in limiting C3S formation.

Usually the economic case for using alternative materials containing

these elements is overwhelming and in many cases a fall in quality
is regarded as an acceptable price to pay. However, in many cases
there are solutions available which will compensate for the quality
loss when using waste streams. For example it has been well
documented that the use of fluorine as a mineraliser in the case of
high levels of sulphate can facilitate the lower temperature
formation of C3S and produce a cement of higher quality than
without these two components. Similarly it was demonstrated over
50 years ago that raw materials in Uganda containing high levels of
phosphate could successfully be used to produce satisfactory quality
cements if the fluorine which was also present in the raw materials
was maintained in the clinker.

Preliminary laboratory trials by this author have also indicated that

mixes containing levels of phosphorous, boron or strontium which,
without other addition, prevent adequate combination can be
satisfactorily combined if a proportion of fluorine can be introduced
and maintained in the clinker.

Modern cement clinker making entails a number of restrictions

which are to the benefit of the environment but with which previous
generations have not needed to contend. The economic and
environmental benefits of using waste streams which would
otherwise be landfilled or incinerated are great. Their use does not
mean necessarily, however, that quality of the product needs to
suffer.

A Harrisson 2011