Indian Journal of Engineering & Materials Sciences

Vol. 17, August 2010, pp. 282-288

Effect of basalt on the burnability of raw meal of Portland cement clinker
H El-Didamony
a
, A Abdel Rahman
b
*, F Nassar
b
& M Saraya
b

a
Faculty of science, Zagazig University, Zagazig, Egypt

b
Faculty of Science, Al-Azhar University, Cairo, 11884, Egypt
Received 17 February 2009; accepted 24 May 2010
This study presents the effect of basalt as a flux and mineralizer on the formation of Portland cement clinker fired at
different temperatures. Five mixtures are prepared by addition of different amounts of basalt such as 0.0, 2.5, 5.0, 7.5 and 10.0
mass % to the kiln feed prepared for the ordinary Portland cement clinker manufacture. Each mixture from the above mixes is
molded in one inch cylindrical bar under 300 kg/cm
2
and fired in muffle furnace at different firing temperatures such as 1200C,
1300C and 1350C for 2 h as soaking time. The fired clinker is quenched in the air to prevent the dissociation of the formed
clinker. The degree of clinkerization is studied by the determination of insoluble residue, free lime contents and the
identification of mineralogical phases such as C
3
S, -C
2
S, C
3
A and C
4
AF by XRD analysis. The potential phase composition of
clinker is also calculated by the modified Bogue formulae. The hydration characteristics are investigated by the determination of
free lime, combined water contents, total porosity, bulk density and compressive strength for all clinkers fired at different
temperatures. In addition, IR spectra of hydrated cement pastes of some selected samples are studied.
Keywords: Basalt, Burnability, Portland cement clinker

The addition of small amounts of some substances that
are not normal clinker raw meals may distinct alter the
progress of the clinkerization processes. These
substances that have the capacity to intensify the rate of
clinker formation are called fluxes or mineralizers.
The use of fluxes and mineralizers to facilitate of
clinkerization was studied by adding some compounds
in the ordinary cement raw meal. Among these
compounds, fluorides and silicofluorides have been
studied more, although they have rarely commercially
survived, owing to the rapid deterioration of refractory
kiln lining and the effects on setting time and strength
1-3
.
A fluxing agent or fluxes are substances that
accelerate the formation of clinker by decreasing the
temperature at which a melt starts to be formed in the
system and by an increase of the amount of the liquid
phase at any temperature above. Under these
conditions, tricalcium silicate (C
3
S) starts to form at a
lower temperature; the reaction progress faster and the
clinkerization process may be completed at a
temperature much lower than that need in the absence
of the fluxing agent.
Unlike fluxing agents, mineralizers are substances
that accelerate the rate of solid-state reaction or reactions
that take place within the liquid phase or at liquid-solid
interface without significantly altering the temperature
of melt formation and the amount of melt present.
In the presence of mineralizers/fluxes, the viscosity
and surface tension of the formed melt may be also
altered. Generally, the rate of clinkerization accelerates
as viscosity declines and surface tension increases
4,5
.
There are many studies to use basalt as an aggregate
for concrete. The physico-mechanical properties of
basalt can be summarized as
6
: compressive strength
(MPa) 158, tensile strength (MPa) 12.2, specific
gravity 2.8 and absorption (%) 1.4.
Basalt is basic rock, poor in silica and alkalis and
rich in magnesium, iron and calcium
7,8
. The results
show that basalt is by far the most reactive of
aggregate studies. Ions were both released and
absorbed by this aggregate; possibly indicating that
hydration of the surface layer had taken place
9
.

Experimental Procedure
The materials used in this study were raw meal
(kiln feed), and basalt which dry ground in an
automatic agate mortar. Table 1 shows the grain size
distribution of these materials.
_________________
*Corresponding author (E-mail: adel1697@yahoo.com)
Table 1 Sieve analysis of starting materials (wt% w)
Sieve
Materials
> 150 m 150 m-
106 m
106 m-
90 m
90 m-
75 m
75 m-
63 m
<63 m
Kiln feed 5.50 33.39 26.67 13.60 5.16 15.69
Basalt 27.91 14.00 32.20 19.53 4.60 1.74
EL-DIDAMONY et al.: PORTLAND CEMENT CLINKER


283
The chemical analysis of the raw materials was
conducted using conventional wet method as well as
X-ray fluorescence technique as shown in Table 2.
The mineralogical composition of basalt is
identified using X-ray diffraction. Figure 1 shows the
mineralogical composition of basalt sample. It is clear
that it composes from plagioclase, orthoclase, aguite
and goethite.
Five mixtures were prepared by the addition of
different amounts of basalt such as 0.0, 2.5, 5.0, 7.5
and 10 % w/w to the kiln feed prepared for the
ordinary Portland cement clinker manufacture. The
mix composition and the LSF of these mixes are
shown in Table 3.
Each mixture from the above mixtures was molded
in one inch cylindrical bar under 300 kg/cm
2

compressive load. Four cylindrical bars from each
mix (120-139 g) were fired in a muffle furnace at
different firing temperatures such as 1200C, 1300C
and 1350C with a heating rate of 8C for 2 h as a
soaking time. The fired clinker was quenched in the
air to prevent the dissociation of the formed clinker.

Results and Discussion
Basalt is one of the igneous rocks, which is formed
during the cooling and recrystalization of magma in
the old geological ages of earth. Basalt consists of a
remarkably number of common minerals, such as K-
feldspars, plagioclase and anigorite. Also, it contains
some minor minerals such as talc, goethite, halloysite,
olivine and magnetite. Most of these minerals are
cattier of SiO
2
, Al
2
O
3
, FeO, Fe
2
O
3
, MgO, K
2
O and
Na
2
O as shown in Table 2, in addition to small
amounts of trace elements such as Mn, Cu, Cr, Ti, Ni,
Co, V, Sr and Ba. Basalt contains about 9-10% CaO
(not as CaCO
3
), most of them concentrated in
plagioclase and pyroxenes minerals
10-12
.
The presence of different modifications of iron
oxide in basalt influences considerably its reactivity,
which increases, especially in the presence of FeO,
which is an active mineralizer that accelerates the
dissociation of CaCO
3
. Basalt also contains high
amount of iron and aluminum oxides, which increase
the C
4
AF, and C
3
A phase in the produced clinker.
Higher concentration of alkalis in basalt will also
improve the burnability as they act as fluxes. Basalt
contains about 5% MgO, which decreases the liquid
phase viscosity and provides the formation of the liquid
phase at lower temperature in addition the amount of the
liquid phase increases. This factor plays an important
role in the acceleration of clinker phase formation.
Basalt contains also small amount of transition elements,
which affect the rate of clinker phase formation. It is
clear that the addition of different amounts of basalt to
the raw feed change the chemical composition of the
raw mix. The silica, alumina, ferric oxide, magnesia,
Na
2
O and K
2
O increase with the increase of basalt
content. This is due to the increase of these oxides in
basalt in comparison to the raw feed. On other side the
CaO decreases with basalt content due to the decrease of
CaO in basalt in relation with that of the raw feed. Also
from Table 3, an addition of 2.5 and 5.0% basalt on the
kiln feed to prepare raw mixes (M2 and M3), the
Table 2 Chemical analysis of starting materials (wt%)
SiO
2
Al
2
O
3
Fe
2
O
3
CaO MgO SO
3
Na
2
O K
2
O Cl
-
I.L
950C
Total
Kiln feed 13.58 3.77 2.21 41.88 1.35 0.38 0.36 0.29 0.24 35.94 100
Basalt 50.35 14.43 12.75 10.18 6.05 0.11 1.88 1.04 0.15 1.90 99.71


Fig. 1 XRD patterns of basalt rock

Table 3 Composition, chemical and sieve analysis and LSF for
the prepared mixtures
Mix No. Mix 1 Mix 2 Mix 3 Mix 4 Mix 5
Kiln feed,% 100 97.50 95.00 92.50 90.00
Basalt, % 0.00 2.50 5.00 7.50 10.00
LSF 1.02 0.88 0.85 0.78 0.75
SiO
2
13.58 14.51 14.90 15.71 15.96
Al
2
O
3
3.77 4.04 4.29 4.48 4.66
Fe
2
O
3
2.21 2.39 2.62 2.87 3.02
CaO 41.88 41.91 40.01 39.62 38.91
MgO 1.35 1.52 1.59 1.61 1.64
SO
3
0.38 0.36 0.35 0.35 0.34
Na
2
O 0.36 0.41 0.45 0.49 0.52
K
2
O 0.29 0.30 0.31 0.31 0.32
Cl
-
0.24 0.23 0.23 0.23 0.23
LOI
950 C
35.94 34.99 34.35 34.33 34.32
>90 m 18.50 % 18.00 % 13.50 % 13.00 % 13.00 %
INDIAN J. ENG. MATER. SCI., AUGUST 2010


284
chemical composition of raw mixes changes due to the
increase in the A
2
O
3
, Fe
2
O
3
, MgO, alkalis and traces of
transition elements content, therefore the values of LSF
decrease to 0.88 and 0.85 respectively. SM and AM lead
to improve the burnability of raw mixes, reduce the melt
point of liquid phase and maximum amount of liquid
phase at lower temperature. These additions reduce the
free lime content in the produced clinker and increase
the clinker phases.
Addition of 7.5% and 10% basalt on the kiln feed
to prepare raw mixes (M4 and M5) tends to decrease
the value of LSF to 0.78 and 0.75 respectively, as well
as SM and AM. However these high amounts of
basalt reduce the lime content and increase the Al
2
O
3

and Fe
2
O
3
contents in the raw mixes, which lead to
the consumption of high amount of lime to produce
C
3
A and C
4
AF. Therefore, these raw mixes become
not suitable to produce clinker phases, especially alite
C
3
S (OPC) or to produce belite cement.
The mineralizing effect of basalt on raw mixes M1-
M5 which fired at different temperatures such as
1200C, 1300C and 1350C for 2 h soaking time to
show the rate of clinker formation. This was
investigated by determination of free lime and
insoluble residue as well as the formed cement phases
using XRD technique.

Free lime contents and insoluble residue contents
The free lime contents of the fired raw mixes
(M1-M2) containing different amounts of basalt such
as 0.0, 2.5, 5.0 , 7.5 and 10.0% w/w and fired at
different temperatures, are graphically plotted as a
function of firing temperature and mix composition as
shown in Fig. 2.
Figure 2 shows that the free lime contents in the
samples fired at different temperatures, which are an
indication of the progress of clinkerization, decrease
with firing temperature. Also, the free lime contents
decrease with the amount of basalt in the raw mixes.
When the raw mixes fired at 1200C, the free lime
contents are still high. This possibly means that the
firing temperature is insufficient to complete the
clinkerization process. But, at the same temperature
when the amount of basalt increases in the raw
mixes the amount of free lime contents decreases.
This result shows the effect of the basalt as
mineralizing materials as well as decreases the LSF
value. Therefore, the free lime content decreases.
Also, at firing temperature 1300C, the free lime
contents are also high especially in raw mix M1
(0% basalt), but lower than at 1200C. This indicates
the progress of clinkerization process with the firing
temperature as well as the increase of the amount of
basalt decreases the LSF value. When the firing
temperature is 1350C, the free lime contents in the
fired raw mixes decrease to lower limits, especially
in the raw mixes containing high percentages of
basalt. But, the free lime is still high in the raw mix
M1 (0 % basalt). This means that the raw mix M1
needs high temperature, to produce PC clinker with
suitable free lime content, than the raw mixes with
different percentages of basalt. The free lime
decreases with the content in the raw mix due to the
mineralizing effect of basalt, which increases the
amount of liquid phase and improves the clinker
phase formation.
The insoluble residue decreases with the firing
temperature as shown in Fig. 3. Also, the insoluble


Fig. 2 Free lime contents of raw mixes fired at different
temperatures


Fig. 3 Insoluble residue of cement raw mixes fired at different
temperatures
EL-DIDAMONY et al.: PORTLAND CEMENT CLINKER


285
residue increases with the amount of basalt in the
raw mixes, especially M4 and M5. It is clear that
the insoluble residue of the fired clinkers decreases
with basalt content up to 5.0% and then increases
up to 10% at all firing temperatures. Also the rate
of the decrease of insoluble residue is the same at
0.0, 2.5 and 5.0% basalt and it changes to higher
values of basalt such as 7.5 and 10%. Raw mixes
with 0.0, 2.5 and 5.0% basalt show a sharp decrease
of insoluble residue from 1200 up to 1300C. At
1350C, the insoluble residue content is nearly
disappeared in the above clinkers up to 5.0% basalt.
This shows the effect of basalt as mineralizer in the
clinker formation especially with lower value up to
5.0%.
As the amount of basalt increases such as 7.5 and
10.0% the insoluble residue increased with basalt
content at all firing temperatures. The decrease of
LSF tends to increase the insoluble residue in the fired
clinkers. Also, the rate of clinker formation in these
raw mixes is slower than those with lower values of
basalt from 1200C up to 1300C. As the firing
temperature increases the rate of the decrease of
insoluble residue is sharply diminished due to the
increase of the melt content. As the basalt increases
the Al
2
O
3
and Fe
2
O
3
increases, therefore the melt
formation enhances. From these findings it can be
concluded that the addition of basalt up to 5% to the
raw mix increases the formation of clinker at lower
temperature than the original mix. The increase of
insoluble residue with basalt content is due to the
decrease of lime content which reacts with silica to
form C
3
S and -C
2
S.

Phase composition of the fired raw mixes (M1-M5)
Figure 4 illustrate the XRD patterns of the fired
clinkers (M1-M5) for 2 h at 1200C. It illustrate a
single peak at 32.22 and 37.40 (2), indicating the
presence of free lime in the all mixes in a decreasing
order M1>M2>M3>M4>M5.
Also Fig. 4 shows the presence of a single peak at
29.4 (3.03), 32.3 and 34.2 2 indicating alite phase
in a small amount in M4 and M5. It is clear that the
formation of calcium hydroxide at 18.2, 2 is mainly
due to the hydration of free lime. The free lime is still
present after firing at 1200C as well as Ca(OH)
2
in
all mixes. This means that the firing temperature at
1200C is insufficient for firing of Portland cement
clinker. The -C
2
S is the major phase at this
temperature. As the amount of basalt increases the
free lime decreases and the clinker phases such as C
3
S
(alite) and -C
2
S (belite) increase. This mainly due to
the mineralizing effect of basalt as well as the
decrease of LSF. Also, the silica in basalt is found in
the combined state. Therefore, the reactivity of the
formation of clinker in the presence of basalt
enhances.
Figure 5 shows the XRD pattern of the clinkers
fired at 1350C for 2 h. This figure shows
increasing of belite phase with basalt content and
the alite decreases, especially at 7.5 and 10.0%
basalt. The belite is the major phase in the clinkers
M4 and M5. These clinkers are of low heat Portland
cement.


Fig. 4 XRD pattern of cement raw mixes fired at 1200C for 2 h



Fig. 5 XRD pattern of cement raw mixes fired at 1350C for 2 h
INDIAN J. ENG. MATER. SCI., AUGUST 2010


286
Calculated phase composition in the fired clinkers
The calculated phases of the clinkers fired at
different temperatures with various amounts of basalt
(M1-M5) are seen in Table 4.
It is clear that the ferrite and aluminate phases are
nearly the same at 1200, 1300 and 1350C. This is
mainly due to that the formation of these phases
appears at low temperatures from 850C up to
1200C. On the other side, as the amount of basalt
increases the amount of aluminate and ferrite phases
increase due to the increase of Al
2
O
3
and Fe
2
O
3
in
basalt than in clay.
The alite phase starts to form at 1200C in mixes
M1, M2, M3 and M4. Sample M5 has no amount of
alite due to the decrease of LSF. Also, as the basalt
content increases the alite content decreases. As the
firing temperature increases the alite content increases
but also decreases with basalt content in the M1-M5.
Mix sample M2 with 2% basalt shows the higher
value of alite at 1350C. This means that 2.5% basalt
acts as a good mineralizer in the formation of Portland
cement clinker with higher values of alite.
The higher values of belite are formed in all clinker
fired at 1200C. Also, the belite content increases
with the amount of basalt. As the firing temperature
increases up to 1300C the belite decreases due to the
increase of alite content on the expense of belite.
Samples fired at 1350C show nearly the same
amount of belite. Only 2.5% basalt increases the
amount of alite on the expense of belite at 1350C.

Hydration of Portland cement clinkers (M1-M5)
The kinetics of the hydration of the prepared
cements fired at different temperatures are studied by
the determination of the liberated free lime and
chemically combined water contents of cement pastes
up to 90 days. The physico-mechnical properties such
as bulk density, total porosity and compressive
strength of hardened cement pastes are also
determined as a function of curing time and basalt
content for all cement paste samples especially for
clinkers fired at 1350C because at this firing
temperature the clinkers gave lowest free lime content
and highest main clinker phase formation.

Free lime contents
The free lime contents of cement pastes of clinkers
(M1-M5) fired at 1350C and hydrated for 3, 7, 28
and 90 days are graphically represented as a function
of curing time up to 90 days in Fig. 6.
The results show that, the free lime contents of the
hardened cement pastes increase with curing time up to
90 days. This is due to the continuous hydration of the
main cement phases such as C
3
S and -C
2
S that liberating
free lime during the hydration. Also, the free lime
contents of cement pastes of clinkers M2 and M3 is
higher than those of other cement pastes. This is mainly
due to the increase of the C
3
S and -C
2
S in these clinkers
as a result of addition of basalt as mineralizer. On the
other side the cement pastes of clinkers M2 which
contains 2.5% basalt, liberates high amount of Ca(OH)
2
at
all curing times. This fact indicates that the 2.5% basalt is
the optimum amount of basalt as mineralizer. Also, the
free lime content decreases with the basalt content and the
LSF decreases which is proportion to the amount of alite.
Alite gives higher values of free lime than belite.
Table 4 Phase composition of Portland cement clinkers (M1-M5) fired at different temperatures (mass %)
1200C 1300C 1350C


c
l
i
n
k
e
r
Alite Belite C
3
A C
4
AF Alite Belite C
3
A C
4
AF Alite Belite C
3
A C
4
AF
M1 22.60 47.87 10.43 7.45 46.04 30.20 10.43 7.46 41.20 33.79 10.46 8.18
M2 23.39 51.68 11.42 7.85 42.82 36.29 11.42 7.85 53.10 28.63 11.54 8.45
M3 19.14 56.23 12.46 8.49 34.73 42.86 12.46 8.49 36.88 42.88 12.46 9.25
M4 13.63 63.00 12.68 9.76 22.37 56.14 12.68 9.32 24.05 63.94 13.00 10.03
M5 0.00 67.10 13.43 9.76 13.22 65.55 13.43 9.76 14.87 63.35 13.44 10.47


Fig. 6 Free lime contents of hardened cement pastes of clinkers
(M1-M5 fired at 1350C as a function of curing time
EL-DIDAMONY et al.: PORTLAND CEMENT CLINKER


287
The chemically combined water of the hydrated
cement pastes up to 90 days of clinkers (M1-M5)
fired at 1350C are graphically plotted as a function
of curing time in Fig. 7.
It is clear that the cement pastes of clinkers M2 and
M3 give higher values of combined water. This is due
to the high amount of C
3
S in the fired clinkers. On the
other side as the amount of basalt increases the
combined water content decreases due to the
decreases of LSF and then C
3
S.

Bulk density and total porosity
The bulk density and total porosity of hardened
cement pastes of clinkers (M1-M5) fired at 1350C
and hydrated to 90 days are graphically presented as a
function of curing time in Figs 8 and 9.
From these figures, it is clear that the bulk density
increases and the total porosity decreases with curing
time. This is mainly due to the progress of hydration
process. The hydration products fill a part of the pores
therefore the density increases and the total porosity
decreases.
The hardened cement pastes of clinker M2 gives
higher values of bulk density and lower total porosity
up to 90 days than those of the other clinkers. As
amount of basalt increases the density decreases and
the total porosity increases due to the decrease of
LSF, which increases the amount of belite on the
expense of alite. Belite has lower rate of hydration
than alite phase.
The compressive strength of hardened cement
pastes of clinkers (M1-M5) fired at 1350C is shown
in Fig. 10. It is clear that the compressive strength of
cement paste increases with curing time for all cement
pastes. As the firing temperature increases the clinker


Fig. 7 Chemically combined water contents pastes of clinkers
(M1-M5 fired at 1350C as a function of curing time



Fig. 8 Bulk density of hardened cement pastes of clinkers
(M1-M5) fired 1350C as a function of curing time


Fig. 9 Total porosity of hardened cement pastes of clinkers
(M1-M5) fired 1350C as a function of curing time



Fig. 10 Compressive strength of hardened clinkers (M1-M5)
fired 1350C as a function of curing time
INDIAN J. ENG. MATER. SCI., AUGUST 2010


288
phases, especially -C
2
S and C
3
S content increase in
clinker. Therefore it gives high amount of hydration
products, which fill the pores of cement paste and
give high strength. Mix M3 with 5.0% basalt gives the
higher values at all curing times than other mixes.
This is mainly due to the effect of 5.0% basalt as
mineralizer for the formation of Portland cement
clinker, i.e., the silicate phases are well formed. These
phases are the main source of strength. As the amount
of basalt increases than 5.0% the strength decreases
due to the decrease of alite and the increase of -C
2
S,
C
3
A and C
4
AF. The alite is the major phase for the
contribution of compressive strength. Figure 11
illustrates the IR spectra corresponding to hydrated
cement paste M2 (fired at 1350C) cured at 3, 7, 28
and 90 days. The broad band near at 3431.2 cm
-1
and
small band at 1654.1 cm
-1
related to H
2
O. However,
the 3644.6 cm
-1
band of OH
-
in Ca(OH)
2
liberated
during the hydration of Portland cement
13-15
. The
intensity of the 3431.2 and 3644.6 cm
-1
bands
increases with curing time due to the progress of
hydration process. The absorption band 987.4 cm
-1

indicates the formation of CSH, which increase with
curing time. Also, the absorption band at 1458.3 cm
-1

is due to presence of carbonate CO3
2-
.

Conclusions
The results show that the burnability of raw mixes
increases with the basalt content and firing
temperature. The physico-mechanical properties of
raw mix containing 2.5% basalt gives the best
hydration characteristics than the other cement pastes.
This is mainly due to that the amount of 2.5% basalt
is considered the optimum amount of basalt as
mineralizer.

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Fig. 11 IR spectra of hydrated M2 (2.5% BS) as a function of
curing time