92 ICR SEPTEMBER 2004

Concrete petrography is used to diagnose

Concrete petrography

Raw materials for cement making

Optical microscopy in cement and
concrete making begins with examination
of the raw materials for the cement and
the aggregate to make the concrete. The
use of polished and thin sections to
characterise the petrography of rocks is an
essential part of the assessment of
potential resources of materials. Grain size,
porosity and mineralogy can be
determined and predictions made as to
the ease with which the materials can be
prepared for cement making and also the
ease with which the materials will undergo
the chemical reactions necessary to make
cement clinker in the cement kiln.

Optical microscopy

icroscopy has been used as a

routine method of cement and
concrete analysis for many
years. There are established methods of
using the microscope to control the
cement kiln, such as those described by
Ono1 and elsewhere by Chromy2. The
use of the microscope for concrete
petrography has become routine,
especially in the areas of alkali silica
reaction, sulphate attack, cement content
determination and cement type analysis.

Figure 1: thin section of a concrete

sample showing alkali silica reaction due
to the presence of reactive chert

by Nick Winter, WHD

Microanalysis Consultants Ltd
and Arthur Harrisson, Rugby
Cement, UK

Figure 2: typical polished section

of cement clinker etched with HF
vapour. The mid-grey material
arrowed is the epoxy resin
impregnated into the clinker to
maintain its structure during
preparation.

Clinker microscopy is used to assess the

crystal sizes of clinker samples, but more
particularly to unravel the history of the
transition from raw materials to clinker, by
examination of the crystals relationships
to one another and their relative
abundance as well as the particular forms
of some of the crystal types present in
cement clinker. Figure 2 shows the typical
relationships of the main clinker minerals.
The angular brown crystals are C3S, the
rounded blue crystals are C2S, the
interstitial material comprises the minerals
which are molten in the cement kiln
burning zone, the lighter crystals are C4AF

Clinker microscopy

Similarly, aggregate characteristics can be

determined. For example, the form of
silica in rocks is an essential factor in
determining the susceptibility of the
aggregate to alkali silica reaction when
used in concrete. The identification of
potentially soluble silica by petrography
will probably rule out the use of some
materials as aggregate in certain
applications.

Aggregates

problems with concrete once in place. The

examination of concrete cubes from the
test house or of cores taken from actual
structures can show whether problems are
due to alkali silica reaction (as in Figure 1),
sulphate attack, insufficient cement,
excess of water, insufficient compaction,
incorrect type of cement or a host of
other possibilities.

Figure 4: effects of slow cooling in

the cement kiln

to cement and used to make concrete.

Much interpretation can, however, be
carried out using the optical microscope
(two examples are shown in Figures 3 and
4). Figure 3 shows the effect on the
microstructure of insufficiently ground
silica sand. The large ring of blue C2S
crystals occupy the site of a sand grain
which was incapable of conversion to C3S
without excessive overheating because of
the density of the C2S structure.
Figure 4 shows the effect of nonoptimal firing conditions in the cement
kiln. The interstitial crystals which were
seen to be finely intermixed in Figure 2

Figure 3: large cluster of C2S due

to the presence of coarse silica in
the raw feed.

and the darker ones C3A. The brown and

blue colours are created by etching the
surface of the polished section with HF
vapour before examination in reflected
light using a petrological microscope. As
described later, the ability to identify the
components is taken to a further stage
using the Scanning Electron Microscope
(SEM), where the chemical analysis of
individual crystals in the clinker samples
can reveal much about the manufacture
of the clinker and also about the probable
performance of the clinker when ground

This article describes of some various applications of optical microscopy

and, more particularly scanning electron microscopy and is intended to
provide an idea of how the techniques are being used and developed for
the cement industry.

I Under the microscope

LABORATORY TECHNIQUES

CaO
SiO2
Al2O3
Fe2O3

the Bogue calculation with those found in

practice and Table 2 compares the
proportions of the compounds determined
by the different methods. C3S is also
called alite, C2S, belite, C3A aluminate
and C4AF ferrite.
The free lime was measured by wet
chemistry for the first two columns. The
modified Yamaguchi method was
described by Yamaguchi and Takagi4 to
improve the Bogue calculation using
typical analyses for the constituents rather
than the pure compounds compositions.
The differences in the amount of C3S
present, compared to the Bogue
calculation, were appreciable. These
differences can have a real effect on the
quality of cement and the cause of

Bogue Calculation
Alite
Belite Aluminate Ferrite Alite
73.7
65.1
62.3
46.2
72.6
26.3
34.9
0
0
25.8
0
0
37.7
21.0
1.0
0.4
32.9
0
0
0

X-ray microanalysis
Belite Aluminate Ferrite
63.2
56.0
47.4
31.8
4.2
3.8
2.1
31.3
22.1
5.0
19.6
0.8

0.3
100

Point counting
61
22
17

SEPTEMBER 2004 ICR 93

otherwise inexplicably poor strengths of a

cement can be shown by this method.
The next stage is the interpretation of the
result. For example, reducing conditions
may cause Fe2O3 to reduce to FeO,
which replaces CaO in the silicates. This
changes the composition of the C3S and
alters the proportions of the constituents.
As well as alite composition, belite,
aluminate and alkali sulphate compositions
are also of particular interest in assessing
clinker quality. Since X-ray microanalysis
data is quantitative, it can be used for
statistical comparisons of other chemical
or physical parameters of cement, clinker
or works production data such as kiln
temperature or the proportions of fuel
used in the kiln and precalciner; this
approach needs data from clinker samples
taken over a period of time.
In general, the possibilities for both the
improvement of cement performance and
for fundamental studies concerning clinker
formation and properties are increased
with the large volume of data produced
by regular analysis of production clinkers
in this manner (5, 6 and 7).

Bogue Modified Yamaguchi QXDA

57.7
65.6
68.8
18.7
12.7
14.2
9.7
6.0
9.6
9.7
13.1
8.3
(0.7)
(0.7)
Nd
96.5
98.1
101.3

practice. With the actual compositions of

the constituents (averaged from multiple
analyses from many different clinker
nodules) the assumptions usually made
can be improved upon. For example, a
clinker was examined by optical
microscopy, SEM and quantitative XRD
methods3. The proportions of the minerals
present were calculated by each method
and compared to the Bogue calculation of
potential compound composition
assuming pure compounds and
equilibrium cooling.
The results are shown below. Table 1
compares the assumed compositions in

Alite
Belite
Aluminate
Ferrite
Free lime
Total

Table 2: quantitative phase compositions (weight percent)

determined by different techniques

false colour for presentation purposes, but

the subtlety of the grey level differences is
generally of more of benefit to the
experienced operator.
Because the combination of SEM and Xray microanalysis can obtain chemical
analyses of individual crystals in the
clinker, it is a very powerful tool in
determining detailed mineralogy and
therefore potential performance in

Figure 5: backscattered
electron image of a
polished section of a
cement clinker

Table 1: compositions of the phases assumed in the Bogue

calculation and those determined by X-ray microanalysis

Figure 5 shows an image of a cement

clinker in the SEM. In the SEM image, the
different crystals do not have the colours
as are produced by etching the surface in
optical techniques. SEM images are always
black-and-white, although they may be
given false colours. The crystals are
differentiated in the image by grey level;
in the backscattered image, the grey level
of each phase is dependent on the mean
atomic number of that phase.
Although the magnifications usually
employed in SEM examination of polished
sections of clinker is generally similar to
that used in optical work, the resolution of
the electron beam is considerably better
than is possible with reflected light. The
detail on the surface of the crystals is
therefore more pronounced and defects
are seen which might be missed in optical
microscopy. It is of course possible to add

Clinker examination

The scanning electron microscope offers

most of the capabilities of optical
microscopy with the added dimension that
X-ray microanalysis can give analyses of
individual crystals.
The areas where the added capabilities
of the SEM are most apparent are in
cement clinker examination and concrete
petrography and some brief illustrations
follow.

Scanning electron microscopy

(SEM)

are here larger and better formed. This

signifies slow cooling within the cement
kiln, ie: the flame is too far down the kiln
and crystallisation of the liquid has been
allowed to occur at a leisurely pace at
relatively high temperatures. The more
perfect the crystals, in very general terms,
the less reactive will be the cement when
mixed with water. This situation would
therefore generally be regarded as being
detrimental to the quality of the clinker.

LABORATORY TECHNIQUES

94 ICR SEPTEMBER 2004

SEM examination of hardened concrete

can assist with many problems concerned,
for example, with concrete expansion,
cracking or material composition. The type
of cement used, the proportions of each
cementitious component and the degree
of hydration can all be measured. The
water to cement ratio can also be assessed
and the nature of any contaminants
identified.
Figure 6 shows a brief example of the
type of analysis which can be produced.
Alkali-silica reaction has occurred in this
concrete and alkali silica gel has formed
within the aggregate at the lower left, and
been extruded into the resulting cracks
caused by the expansion.
The gel becomes increasingly calciumrich with increasing distance from the
aggregate; the greater the distance from
the aggregate, the older the gel and the
more time it has had to take calcium up
from the surrounding cement hydrates.

Concrete examination

LABORATORY TECHNIQUES

[6] Harrisson, AM, 22nd ICCem Microscopy,

Microscopy, p226, 2001. ______________

[7] Harrisson, AM and Winter NB, 23rd ICCem

p39, 2000.

p338, 1999.

The use of microscopical techniques has a

long track record of problem solving. With
the collection of large amounts of data
from SEM analysis and the manipulation

[5] Harrisson, A.M, 21st ICCem Microscopy,

Vol 1 p181, 1969.

[4] Yamaguchi, Y and Takagi, S in 5th ISCC,

pp775-780. 1985.

Cement and Concrete Research, Vol 15,

[3] Harrisson, AM, Taylor, HFW and Winter NB,

No 8, 1983, pp458-463.

[2] Chromy, S, Zement-Kalk-Gyps, Vol 36,

(1981).

[1] Ono, Y , in 3rd ICCem Microscopy p198

References

Developments

Figure 6: polished section of concrete with

alkali-silica reaction. The X-ray spectra shows
how the composition of the alkali-silica gel
changes with distance from the source
aggregate. At A, near the aggregate, the
young gel contains much potassium and little
calcium, at B, there is more calcium and less
potassium and at C, the older gel is almost
indistinguishable in composition from normal
calcium silicate hydrate (D). Ettringite is visible
in the gap between the paste and aggregate
at the lower right.

of the data by modern computing

techniques, the methods are becoming
increasingly useful as predictive tools,
using results from plant clinkers as well as
from laboratory simulations to create
models of the likely performance of clinker
as cement.