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Bogue
vs Chromy
hy the growing interest in
clinker mineralogy, which has
been substantially understood
for more than 70 years now?
Two factors seem to be driving this
renewed interest.
Firstly, most cement companies wish to
produce more extended cements as this
boosts their production capacity and profits. Cement clinker is partially replaced by
extenders in these cements, and therefore
the clinker produced from the kiln translates into a greater quantity of cement to
be sold. Cements extended with granulated
blast furnace slag, natural and industrial
pozzolans and limestone are also better
than pure Portland cements in many concrete applications. However, as less cement
clinker is present in these cements, the
quality and mineralogy of the clinker
becomes all the more important. Less
hydraulic clinker mineral has to produce
more hydraulic activity, and substandard
clinker quality cannot be tolerated.

by Dr Michael Clark
In Junes Technical Forum the fundamentals of cement clinker phase
equilibria were discussed and subsequently there has been an excellent
response from readers and correspondents to the CemNet Technical Forum.
This is clearly an area of great interest and worthy of further coverage in
this column. There are also an increasing number of articles in
International Cement Review and other journals concerning mineralogy,
and the techniques for measuring and controlling mineralogy.

Secondly, many cement companies are

pursuing a strategy of replacing fossil fuels
with alternatives and by-products of industry and society for firing their kilns. This is
the overriding economic factor justifying
the continued operation of a number of
kilns, as total thermal energy costs can be
reduced (to zero and beyond in the best
cases). Alternative fuels are undoubtedly
here to stay in the cement industry, but do
bring some problems. In many cases they
contain oxides and species not normally
present in cement raw materials and fossil
fuels. These exotic
All kinds of material are bring considered as waste fuels including
oxides and species are
plastics and refuse which will effect clinker mineralogy
incorporated in the
clinker and change
the mineralogy, hence
the renewed interest
in clinker mineralogy
and its control.

Alternative
fuels
Of course there are
other factors driving
the strategies of fossil
fuel replacement and
production
of
extended
cements.
Most readers will be
aware of the growing
emphasis on sustainability of cement
operations, from the

number of articles and papers recently

published following the release of the
WBCSD report Towards a sustainable
cement industry. Alternative fuels and
extended cements among the key means
for cement companies to offset their carbon emissions and improve the sustainability of their operations.

Bogue calculation
So the reasons for the increased interest in
clinker mineralogy are clear. For many
years cement chemists have known that
the Bogue calculation of clinker mineralogy is unsatisfactory and does not represent the real mineralogy of the clinker. In
essence it is a formula for the conversion
of the oxide composition of the clinker
into a theoretical mineralogy, and in fact is
just another way of representing the oxide
composition. It does not relate to the true
mineralogy.
Dr Stanislav Chromy of Brno in the
Czech Republic has been studying and writing papers on clinker mineralogy for more
than 30 years. His findings are that the
true Alite content of cement clinker varies
from 5 to +20 per cent of the Bogue C3S
content, with the Alite content normally
significantly higher than the Bogue C3S
content at the expense of the interstitial
material (C4AF and C3A).
The reasons for this are not hard to
explain. The Alite mineral produced on an
industrial cement kiln is not pure C3S.

INTERNATIONAL CEMENT REVIEW / SEPTEMBER 2002

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the microscope image and subsequent pattern recognition. Using clinker microscopy
for real clinker mineralogy control is therefore possible for all cement factories today.
Having the measurement of true clinker
mineralogy is the key pre-requisite of
clinker mineralogy quality control. Dr
Chromy advocates the following steps to
realise a true clinker mineralogy quality
control system. This system will stabilise
true Alite content and hydraulic performance of the clinker in
Portland
and
extended
cements:
continuously measure clinker
oxide composition and true
mineral
composition
(by
microscopy or XRD and
dynamic Reitveld Analysis)
calculate deviation from target clinker mineral composition
translate this into a deviation from clinker chemistry
Bogue modificatargets (LSF, SM etc)
tions
adjust kiln feed chemistry
The reasons for variance
Environmental regulations are causing cement manufacturers to look closely
targets to correct deviations of
between the Bogue mineralogy
at emissions and therefore also clinker mineralogy
clinker mineralogy from target
and true mineralogy are there control kiln feed chemistry
fore well documented in the
to these modified targets.
However, there are drawbacks. XRD and
literature, and the Bogue calculations can
Adoption of this true clinker mineralogy
dynamic Reitveld Analysis remain expenbe modified to take these factors into conquality control regime leads to further
sive options and more industrial applicasideration. However, the modifications are
cross-checks and calibration possibilities
tions and references will be needed before
complex making it difficult for a cement
to enhance the quality control:
the technique is widely employed in indusfactory to take this into consideration in
as the clinker oxide composition and true
trial clinker quality control. The problem
hour-to-hour and day-to-day clinker quality
mineral composition are known, the relawith clinker microscopy has long been the
control. Thankfully, expert systems giving
tionship between the two can be deterneed for skilled operators and technicians
good agreement with true mineralogy have
mined by multiple regression techniques
to prepare the clinker for examination
now been developed. These allow true min the coefficients representing this relaunder the microscope, and interpret the
eralogy to be predicted from the full analytionship can be continuously kept in caliresults. With less and less people employed
sis of the clinker including all minor combration as new measurements become
on cement factories these skilled persons
ponents.
available
are simply not available to make these
when true mineralogy measurement is
measurements in shift control laboratories.
Dr Chromys approach
not available, due to equipment mainteAgain help is at hand with automated samReal mineralogy prediction is only a first
nance or failure, the true mineralogy can
ple preparation, photographic capture of
step however. Alfredo Santos-Arceo and
be estimated using the calibrated multiple
Clinker microscopy for real clinker minerology control is a valuable tool
relationship with oxide composition.
These Colombian conversions avoid the
use of Bulgarian constants to convert from
oxides to clinker mineral composition.
All the elements and building blocks of
these Dr Chromy total clinker mineralogy
control systems are now available for those
cement companies who are serious about
maximising product quality and minimising
the variation of their cement performance.
With this approach it should be possible to
finish using Bogue calculations and adopt
the Dr Chromy approach to clinker mineralogy and quality control. _____________
Substantial quantities of oxides other than
CaO and SiO2 are contained in this
industrial Alite in solid solution. It is not
surprising that the Alite content is boosted
by this solid solution at the expense of
interstitial material, as the Al2O3 and Fe2O3
contained in solid solution increases the
proportion of the total present as Alite,
and leaves less Al2O3 and Fe2O3 available
for formation of the C4AF and C3A which
make up the interstitial material.
Further deviations from
Bogue C3S content arise
because of non-equilibrium
cooling in an industrial cement
kiln, the solid solution of trace
oxides not considered in the
Bogue equation, and fundamental alteration of the CaOSiO2-Al2O3 phase diagram by
some species, most notably
CaF2.

66

Conrado Gaytn of Cemex have recently

echoed the long held belief of Dr Chromy
that What is not measured, cannot be
controlled. Along with Dr Chromy they are
strong advocates of employing clinker
microscopy to measure and control the real
mineralogy of clinker. There are also a
growing number of papers on the possibilities of XRD and dynamic Reitveld Analysis
to achieve the same goal of measuring and
controlling real clinker mineralogy.

INTERNATIONAL CEMENT REVIEW / SEPTEMBER 2002