You are on page 1of 5

p110

114

Hill Microscopy

24/3/04

3:58 pm

Page 1 Production Work in Progress:a.FINAL APRIL ICR:p112

Clinker Microscopy F

CLINKER MICROSCOPY

I The value of microscopy


by Linda M Hills,
Construction Technology
Laboratories, Inc, USA

Evaluation of clinker using microscopy is a powerful technique that can


help improve clinker production and cement quality. One can gather
remarkable information about clinker history as well as provide
information about cement performance. The key to using the microscope is
understanding the process of clinker manufacture: how raw materials are
transformed into clinker. The transformation involves both chemical and
physical processes, as the material passes through the kiln system. Based
on understanding of the process of clinker formation, interpretation of the
microstructure can be used for quality control, troubleshooting, and to
monitor process changes at the cement plant.

Other phases react more slowly. The


characteristics of these phases will
influence how the cement performs at
later ages.

xamining clinker by microscopy is a


powerful technique that can help
improve clinker production and
cement quality. One can gather
remarkable information about clinker
history as well as cement performance.
Clinker microscopy can provide
information about the temperature profile
in the kiln and provide clues to improve
clinker grindability, optimise raw feed
fineness, or increase 28-day strength. For
troubleshooting, imagine being able to
help identify the causes of poor clinker
grindability or low cement mortar strength
with a few minutes lab work! Small
wonder that clinker microscopy has
become an essential tool at so many
cement plants.
How microscopy can reveal so much
about clinker production?
The crystal microstructure of clinker is
formed by everything that goes into it and
what happens to it along the way. In other
words, there is a relationship between
clinker microstructure, the kiln feed, and
burning conditions. Therefore the
microscope can monitor process changes,
troubleshoot problems with kiln operation,
evaluate new raw materials, etc.
How microscopy can reveal so much
about cement performance?
Certain phases react quickly with water
and are important for water demand, early
strength, and setting time. The abundance
of these phases, as well as their crystal
size, morphology, and distribution will
influence how these phases hydrate, and
therefore affect the cements early
performance.
110 ICR APRIL 2004

Clinker formation
The basic process of portland cement
manufacture is the combination of silica
with calcium to produce hydraulic
compounds.
The transformation of the raw materials
into clinker involves both chemical and
physical processes as the material passes
through the kiln system. Burnability of the
raw material is one important aspect of
the chemical processes it defines how
easily the raw materials are transformed
into the desired clinker phases throughout
the clinkering reactions. Physical processes
of clinker production include the formation
of clinker nodules.
Raw materials
The raw materials used are designed and
proportioned to provide the appropriate
amounts of the various clinker phases. The

most abundant phases are termed alite


and belite. Alite is impure tricalcium
silicate, generally termed C3S. Belite is
impure dicalcium silicate, normally termed
C2S. Other phases present in typical
clinker are in the matrix or interstitial, and
commonly contain aluminate (C3A) and
ferrite (C4AF).
In order to generate the desired
amounts of the hydraulic compounds in
the cement, the cement plant chemist
needs to choose the raw mix components
carefully. The available geologic materials
at the plant location will generally dictate
the type and amount of components
required. Given that the primary
constituent of cement is calcium, the main
raw material used is limestone. Shale or
clay is also a common component, used
for its silica and aluminum content. In
order to obtain enough silica, many plants
may also have to use sand. Other
materials that may be used include iron
ore, slag, fly ash, etc. The chosen raw
materials are ground prior to introduction
into the kiln system.

Table 1: burnability insight into the effect of raw material


properties on the resulting fee lime on a relative basis
CaO1400C =[ 0.343(LSF-93) + 2.74(SR-2.3)] + [0.83Q45 + 0.10C125 +0.39R45]
Where:
CaO1400C = is the free lime after burning for 30 minutes at 1400C
LSF = %CaO/(2.8%SiO2+1.18%Al2O3+0.65%Fe2O3)
SR = % SiO2/(% Al2O3+% Fe2O3)
Q45 = % quartz grains coarser than 45m
C125 = % calcite grains coarser than 125m
R45 = % other acid insoluble minerals, (i.e. feldspar) coarser than 45m

p110

114

Hill Microscopy

24/3/04

3:58 pm

Page 2 Production Work in Progress:a.FINAL APRIL ICR:p112

Clinker Microscopy F

CLINKER MICROSCOPY

Figure 1: depiction of clinkering reactions ,


illustrated by Wolter(4)

Burnability
Burnability is the ease with which the raw
materials are transformed into the desired
clinker phases, and is commonly measured
by the amount of free (unreacted) lime
remaining in the clinker (low free lime
indicates an easy-to-burn mix). The
burnability of a raw mix is determined by
its chemical composition, mineralogy of
the raw materials, and its fineness. A
number of equations relating the free lime
after laboratory burns under various
conditions to the composition of the raw
mix and and the fineness of certain

minerals are described in the literature


(1,2). One such is the burnability equation
developed at FLSmidth laboratories,
provided below (3). The importance of a
burnability equation is not to provide an
exact value of the free lime of clinker
made from a given raw mixture; it is more
important that it gives insight into the
effect of raw material properties on the
resulting free lime on a relative basis. See
Table 1
The first part of the equation represents
contribution from the chemical properties
of the raw mix. The LSF (lime saturation

factor) represents the CaO of the mix,


while the SR (silica ratio or modulus) is
related to the amount of liquid phase at
the burning zone temperature. Decreasing
the SR is equivalent to increasing the
amount of liquid phase, and since the
liquid is the transport medium for the
reactants, more liquid can transport more
reactants during a given time and, as a
result the burnability is improved. Note
the relative magnitude of the coefficients
for LSF and SR; the role of the liquid for
the clinker reactions is important, not only
for the chemical reactions but also for the
formation of clinker nodules.
The second part of the burnability
equation represents the contribution to
the burnability from the mineralogy and
fineness of the raw mix. The amounts of
coarse particles represented by C125 , Q45
and R45 are determined by the overall
fineness of the raw mix on the one hand,
and the mineralogical properties of the
raw materials on the other. The different
mineralogy of the mix components leads
to differences in grindability, which in turn
will result in variations in the chemical
composition of the different size fractions
of the raw mix. For example, since quartz
is hard to grind, the SiO2 content of the
coarser fraction of the mix will normally

Figure 2: from raw feed to final product, the clinker production process is outlined by the following sequence of events.
Diagrams are simplified for illustrative purposes.

Cross-section of view of kiln

Nodulisation process

Clinkering reactions

APRIL 2004 ICR 111

p110

114

Hill Microscopy

24/3/04

3:58 pm

Page 3 Production Work in Progress:a.FINAL APRIL ICR:p112

Clinker Microscopy F

CLINKER MICROSCOPY

Figure 2 continued : raw feed to final product the clinker production process
Cross-section of view of kiln

be higher than the finer fraction. Note


that the quartz fineness is more significant
than fineness of other materials, as
indicated by its larger coefficient in the
equation.
Clinkering reactions
The clinkering reactions encompass the
process of transforming the raw mix to
clinker. Figure 1 depicts clinkering
reactions illustrated by Wolter4.
Nodule formation
The physical formation of clinker into
clinker nodules involves agglomeration
due to capillary forces of the clinker liquid.
The agglomeration process is a function of
amount of liquid, particle size, and rate of
kiln revolution.
At around 1250C in the kiln, the clinker
melt forms. At this time, particles and
liquid are present. The surface tension of
the liquid keeps the particles together. If
the amount of liquid is too small, unnodulised material will remain (dust). If
the amount of liquid is too large, the
materials will stick together in a large
mass. The size of the particles being held
together is important, as the surface
tension of the liquid phase will not hold
together coarse particles. While this melt
112 ICR APRIL 2004

Nodulisation process

Clinkering reactions

is being formed and holding together the


particles, the rotating kiln forms nodules
by coalescence of agglomerates and by
layering of fine particles on existing
nodules.
At the same time, an adverse process is
going: the formation and sintering of C3S.
When two C3S crystals come together,
they have a high probability of growing
together to form coarse C3S particles. If
these particles become too large,
nodulisation will be adversely affected.
From raw feed to final product, the
clinker production process is outlined by
the sequence of events shown in Figure 2.
Diagrams are simplified for illustrative
purposes.

Under the microscope


Observation of clinker
Probably the most common method of
evaluating clinker is by polished section.
With this method, the clinker, either
whole or partially crushed, is impregnated
in epoxy. The section is cut to reveal a
cross section, then ground and polished.
To reveal the various phases, the section is
usually chemically etched. Two of the
easiest and safest etches are water and
nital (one per cent nitric acid in 99 per
cent isopropyl alcohol). Exposure to warm

water (40C) for 5-0 seconds reveals


brightly coloured free lime. A water etch
may also be used to observe the
aluminate and ferrite phases. A section
immersed in nital colours the silicate
phases. For additional etch techniques, see
Campbell5.
The prepared polished section is
observed with a polarised-light microscope
using reflected light. Magnifications
between 100x and 600x are commonly
used. The phases that can be observed
include: alite, belite, ferrite, tricalcium
aluminate, periclase, free lime, alkali
aluminate, alkali sulphate, and calcium
sulphates. The important properties of
these phases to evaluate include size,
morphology, distribution, and reactivity to
etchants. Porosity of the clinker should
also be noted (see Figure 3).
Observations and clinker formation
With an understanding of the physical and
chemical clinkering reactions, microscopic
observations can be related to these
processes. For example, a high free lime
content in the clinker can indicate that the
raw mix was not chemically formulated
correctly, the mix was improperly burned,
the mix was inhomogeneous, or there
were coarse calcite particles in the mix.

p110

114

Hill Microscopy

24/3/04

3:58 pm

Page 4 Production Work in Progress:a.FINAL APRIL ICR:p112

Clinker Microscopy F

CLINKER MICROSCOPY

Figure 3

Alite (C3S) normally


hexagonal crystals observed
in cross section,
25-50mm in length.

Belite (C2S) normally 2540mm rounded crystals with


multidirectional lamellae.

Tricalcium aluminate (C3A):


Observed in etched and
polished clinker as blue to grey
angular crystals in the
interstitial. High alumina ratio
will produce greater amount of
aluminate over ferrite.
Ferrite (C4AF): the interstitial
counterpart of the C3A, it is
more reflective than C3A in an
etched polished surface.

The distribution of the free lime can also


reveal information. A tight cluster of free
lime crystals is a result of coarse calcite
particles not having time to fully react
during clinkering and not a result of
improper chemical formulation which
would tend to lead to more well
distributed free lime crystals (Figure 4).
Another example of how observations
of clinker microstructure can be used to
interpret conditions of clinker formation is
the presence of belite clusters. Again, the
burnability of a raw mix is determined by
its chemical composition, mineralogy of
the raw materials, and its fineness. (see
Figure 5).
Clinker parameters and
cement performance
There are many factors to consider when
interpreting cement performance
properties, such as setting time and
strength development. For example,
chemistry, fineness, and sulphate form all
play important roles in setting time.
However, observation of the clinker
microstructure may help to provide
additional clues to cement performance
problems.

It is known that alite is quick to react.


Therefore, properties one can observe in
the microscope to provide clues to early

reactivity and strength problems include


relative or measured alite abundance.
According to Lea6, the strength at any
hydration time increases with increasing
C3S content up to 70 per cent, then tends
to decline at higher amounts. Alite
reactivity can also be observed in its
response to etchants, and is an important
response to observe especially when
comparing samples.
Since belite reacts more slowly than
alite, properties one can observe to
provide clues to later reactivity problems
include belite abundance, morphology,
and reactivity to etchants. Distribution of
belite can influence cement reactivity
indirectly: dense clusters of belite will be
hard to grind, producing coarse particles
of cement; coarse cement particles do not
hydrate as quickly as finer particles,
thereby resulting in decreased cement
reactivity.
Other clinker phases are also important
to cement reactivity and performance. For
example, C3A reacts quickly when
hydrated; its properties are closely related
to setting time. Excessive free lime in the
cement is related to expansion, or
unsoundness - but on the other hand, a
small amount can help avoid overretardation by admixtures.
These are only a few examples of the
correlation between microstructure and

Figure 4

Free lime nest as result of


coarse calcite particle.
Note that shape of nest
retains shape of original
coarse particle.

Smaller well-dispersed
free CaO.
Free CaO
crystals

Photomicrograph
demonstrates reaction
between belite and free
CaO to form alite.
Belite crystals

APRIL 2004 ICR 113

p110

114

Hill Microscopy

24/3/04

3:58 pm

Page 5 Production Work in Progress:a.FINAL APRIL ICR:p112

Clinker Microscopy F

CLINKER MICROSCOPY

Figure 6

Troubleshoot problems
When there is a problem with clinker
production or cement performance, the
clinker microstructure can provide a clue
as to the cause. Again, routine physical
and chemical tests can provide some
insight, but often microscopy can help to
provide a complete solution.
Monitor process changes
If a change in any aspect of clinker
production is anticipated (such as new raw
materials, burner pipe position), analysis
of the microstructure is important before,
during, and after the change. The
operator can pinpoint the effects of the
change, whether positive or negative, and
predict changes in cement performance.
___________________________________I

Acknowledgments
This paper was previously presented at:
"22nd International Conference on
Cement Microscopy" 2000, Montreal,
Canada
Vagn Johansen and Greg Miller are
gratefully thanked for their valuable
contributions and suggestions in the
preparation of this manuscript.
Photomicrograph
demonstrates belite
cluster as result of large
quartz grain.

cement performance; other work includes


a method developed by Ono, which uses
microscopic parameters such as silicate
size, alite birefringence, and belite colour
to predict 28-day strength7. Taylor8 and
Lea6 provide detailed descriptions of
cement hydration, including hydration of
individual phases, which can be used to
interpret microscopic observations to
cement performance.

Conclusion
Role of microscopy at cement plant
As we have seen, there is a relationship
between clinker microstructure, the kiln
feed, and burning conditions. In addition,
since each clinker phase reacts differently
with water, the clinker microstructure can
reveal information about cement
performance. Therefore, clinker
microscopy is a valuable tool at the
114 ICR APRIL 2004

cement plant as a compliment to standard


chemical and physical tests.
Quality control
When clinker microscopy is performed
routinely, operators get to know the
microstructure of the plants typical
clinker. Then, if there is a change in the
microstructure (for example, crystals
become larger, irregular, or poorly
distributed), kiln operators can quickly
react to modify pyroprocessing parameters
to improve clinker quality.
Physical tests, such as strength and
fineness, and chemical tests, such as free
lime, provide valuable, but limited, quality
control information.
The relatively quick preparation time of
clinker microscopy and the wealth of
pyroprocessing information it can reveal
make it a very valuable tool.

References
[1] Fundal E (1979) The Burnability of
Cement Raw Mixes, World Cement
Technology, FLS Review (22)
[2] Miller, FM (1981) Microscopy as an
Aid in Evaluation of Mix Burnability and
Clinker Formation, Proceedings of the
Third International Conference on
Cement Microscopy, pp181-192.
[3] Theisen K (1992) The Influence of
Raw Mix Burnability on the Resulting
Cement Clinker, Proceedings of the 14th
International Conference on Cement
Microscopy, pp74-88.
[4] Wolter, A (1985) Influence of the Kiln
System on the Clinker Properties in
Zement-Kalk-Gips, (10) pp612-614.
[5] Campbell DH (1999) Microscopical
Examination and Interpretation of
Portland Cement and Clinker, Portland
Cement Association, Skokie, IL, pp11-15.
[6] Lea, FM and Hewlett, PC (Eds) (1998)
Leas Chemistry of Cement and Concrete,
4th Edition. London Arnold Publishers.
[7] Ono Y (1995) Onos Method,
Fundamental Microscopy of Portland
Cement Clinker.
[8] Taylor HFW (1990) Cement
Chemistry, New York, Academic Press.