Cement and Concrete Research 59 (2014) 147154

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Cement and Concrete Research

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Evaluation of P2O5 distribution inside the main clinker minerals by the

application of EPMA method
Tom Ifka a,, Martin Palou a, Jan Baraek b, Frantiek oukal b, Martin Boh b
a
b

Institute of Construction and Architecture, Slovak Academy of Sciences, Dbravsk cesta, 9845 03 Bratislava 45, Slovak Republic
Faculty of Chemistry, Brno University of Technology, Purkyova 464/118, Brno 612 00, Czech Republic

a r t i c l e

i n f o

Article history:
Received 17 December 2013
Accepted 28 February 2014
Available online 6 April 2014
Keywords:
Reaction (A)
Microstructure (B)
Ca2SiO4 (D)
Ca3SiO5 (D)
Waste management (E)

a b s t r a c t
The formation of Portland clinker phases has taken place in thermodynamically non-equilibrium state between
macro-oxides CaO, SiO2, Al2O3, Fe2O3 and MgO from raw meal and P2O5 from bone meal. The paper deals with the
study of clinker minerals as solid solutions with P2O5 during the clinkerization of raw mixture containing bone
meal (BM). The ash of BM has contributed as a raw material to the formation of different clinker phases. Electron
probe microanalysis (EPMA) method was used to determine the preferential distribution of P2O5 inside calcium
silicate phases and its inuence upon C2S/C3S ratio. Basing on these results, composition of solid solution of C2S
and C3S was established.
2014 Elsevier Ltd. All rights reserved.

The typical composition of belite (C2S solid solution) is expressed by

formula [1]:

1. Introduction
The use of waste products as partial replacement of fossil fuels in cement manufacturing is well known. These alternative fuels are used
mainly for their caloric values and also because of the similarity between chemical composition of their ashes and raw materials or clinkers. Some alternative fuels can also be considered as alternative raw
materials. The ash as remained inorganic part of wastes after burning
process is incorporated into clinker or reacts with raw material to
form clinker minerals or their solid solutions. One of the alternative
fuels that could be considered as an alternative raw material is the
meat bone meal (MBM).
The ash of the MBM is composed mainly of P2O5 and CaO. P2O5 enters
the clinker minerals forming solid solutions. In solid solutions, the chemical composition varies while the crystal structure remains the same. Solid
solution is formed by the substitution of ions in crystal lattice by other
ions with similar ionic radius. During ionic substitution, the vacancies
can form in normally unoccupied sites. The composition of solid solutions
can be expressed by oxide or elemental analysis. According to [1], the
typical composition of alite (C3S solid solution) with a wide variety of
foreign atoms in its structure can be expressed as follows:
Na0:01 Ca2:90 Mg0:06 Fe0:03 Al0:04 Si0:95 P0:01 O5:00 :

K0:03 Na0:01 Ca1:94 Mg0:02 Fe0:02 Al0:07 Si0:90 P0:01 O3:93 :

The amount of each foreign ion in the structure of calcium silicates

depends upon the amount of the element in question in the bulk composition, but aluminum and iron are always present.
The aluminate phase accommodates alkali metal ions and also a
large amount of another foreign ions. Taylor quotes a typical composition for C3A solid solution [1]:
K0:04 Na0:09 Ca2:73 Mg0:09 Ti0:01 Fe0:17 Al1:66 Si0:17 O6:00 :

Again, the amount of each foreign ion depends upon the amount of
the element in question in the bulk composition, but silicon and iron are
always present.
Of all phases, tetracalcium aluminoferrite has the most variable composition. In addition to its variable aluminium/iron ratio, it can take up
large amounts of foreign elements. Taylor quotes a typical composition for ferrite [1] in clinkers with higher alumina contents:
K0:01 Na0:01 Ca1:98 Mg0:17 Ti0:05 Mn0:02 Fe0:62 Al1:00 Si0:14 O5:00

and for ferrite in clinkers with lower alumina contents:

Corresponding author. Tel.: +421 2 5930 9260.
E-mail address: tomas.ifka@savba.sk (T. Ifka).

http://dx.doi.org/10.1016/j.cemconres.2014.02.010
0008-8846/ 2014 Elsevier Ltd. All rights reserved.

K0:01 Ca1:98 Mg0:17 Ti0:05 Mn0:02 Fe0:90 Al0:72 Si0:14 O5:00 :

148

T. Ifka et al. / Cement and Concrete Research 59 (2014) 147154

Table 1
Chemical composition of used raw materials.
Composition
(wt.%)

Marl

Limestone

Blast furnace slag

Ash of bone meal

CaO
SiO2
Al2O3
Fe2O3
P2O5

18.88
41.80
11.90
3.82

53.67
3.65

8.84
3.20
0.69
80.91
0.20

54.14
0.82

0.01
38.03

Table 2
Adjusted basic chemical parameters.
Raw materials

Raw material
composition
(wt.%)

Characteristics
of cement
raw meal

Mineralogical
composition
(wt.%)

Marl
Limestone
BFS
Ash of BM

28.50
70.25
1.25

LSF
SM
AM
HM

C3S
C2S
C3A
C4AF

93.84
2.64
1.62
2.16

62.69
18.58
8.63
10.11

The ash of MBM contains P2O5 in the form of calcium phosphates.

The inuence of P2O5 or calcium phosphate on the formation, stability
and properties of calcium silicates in Portland clinker has already been
investigated by many authors [26]. It was demonstrated that phosphate takes an active part in the reactions during clinker burning process and shifts the stability limits of individual phases with formation
of solid solutions [7]. During the reaction, P2O5 is rstly xed by calcium
in the form of apatite, which gets unstable at higher temperatures,
reacting with silicon to form an isomorphous mixture made up of
dicalcium silicate and tricalcium phosphate (C2SC3P) rst, which can
be mixed with -C2S continuously. If the CaO supply is sufcient, this
isomorphous mixture containing phosphate can react further to form
alite containing phosphate. The viscosity of the clinker melt is diminished as a result of phosphate input, which is conducive to alite growth.
As phosphate input increases, C2SC3P isomorphous mixtures having a
structure of -C2S and -C2S are formed. As a consequence, alite formation is increasingly impeded [710].
In [11], it is stated that P2O5 enters the C2S structure and PV ion lls
IV
Si position. During this substitution the vacancy is built up as a result
of need to maintain electroneutrality.
II

IV

Ca 2 Si NV0 2 P

The substitution of two PV atoms for two SiIV atoms causes the CaII
atom to leave its position and so the vacancy is created.
General formula of C2S solid solutions with stabilizing P2O5 follows
[12]:
Ca2x=2 V0x=2 Si1x Px O4 ; where 0:02 x0:10:

Fig. 1. Microstructure of the sample with 1.81 wt.%. P2O5 (1st series).

It follows that during the synthesis of stabilized C2S from pure C2S
and P2O5, certain amount of CaO must be released.
Stank and Sulovsk [13] found out that P enters the structure of
both calcium silicates at least partially through the so called berlinite
substitution: AlIII + PV = N 2 SiIV, where AlPO4 (the berlinite component), isostructural with quartz, substitutes SiO4 tetrahedrons.
Benarchid et al. [14] studied the inuence of chromium and phosphorus additions on the thermal decomposition of CaCO3 and the formation of the tricalcium aluminate. They showed that simultaneous
additions of chromium and phosphorus oxides up to 1.41 and
1.31 wt.%, respectively, lower the temperature decomposition of
CaCO3 and improve the burnability of the synthesized doped tricalcium
aluminate. The corresponding reduction of temperature decarbonation
was about 34 C. The same collective of authors [15] also examined the simultaneous inuence of iron and phosphorus inclusions on the CaCO3 decarbonation and the C2S formation in CaCO3SiO2 mixtures around the
molar ratio CaCO3/SiO2 = 2. In these reacting mixtures, the onset temperature of decarbonation decreased with Fe2O3 and P2O5 additions of,
respectively, less than 9.50 wt.% and 8.45 wt.%. The mineralogical
analysis of the synthesized solid solutions (Ca2 2xFexV0x)(Si1 xPx)O4
(V0: cationic vacancy of Ca2+) with 0 x 0.20 showed that at room
temperature the iron and phosphorus doped C2S is stabilized in the
, and forms for additions less than 9.50 wt.% Fe 2 O3 and
8.45 wt.% P2O5.
Another authors [16] studied the effect of combination of manganese and phosphorus elements on the formation of solid solutions, by
heterovalent substitution of corresponding ions (5/2 CaII + SiIV = N2
MnII + PV + 1/2 V0) in C3S lattice, at air atmosphere. These solid solutions were described by the following cationic vacancy formula

Table 3
The free lime content in the clinker.
Calcining temperature:
1450 C

1st series

Calcining temperature:
1450 C

2nd series

Ash of BM
(wt.%)

P2O5
(wt.%)

f-CaO
(wt.%)

Ash of BM
(wt.%)

P2O5
(wt.%)

f-CaO
(wt.%)

0
0.99
1.96
2.91
3.85
4.76

0
0.38
0.75
1.11
1.46
1.81

0.05
0.22
0.97
2.1
3.03
4.08

0
1
2
3
4
5

0
0.38
0.76
1.14
1.52
1.9

0.05
0.05
0.68
1.5
2.17
3.08

T. Ifka et al. / Cement and Concrete Research 59 (2014) 147154

149

Table 4
EPMA line analysis of sample shown in Fig. 1.
Point

MgO
(wt.%)

Al2O3
(wt.%)

SiO2
(wt.%)

P2O5
(wt.%)

CaO
(wt.%)

Fe2O3
(wt.%)

CaO/SiO2

Solid solution

1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25

1.01
1.94
0.803
0.781
1.14
3.00
2.98
2.97
0.596
0.00274
0.00269
2.58
0.772
1.40
0.00277
1.12
0.00258
0.00218
0.502
2.02
1.04
0.749
1.00
1.02
0.00218

1.26
6.35
1.10
1.46
2.12
6.12
16.8
19.8
1.29
1.60
1.85
14.0
2.32
6.23
1.96
3.57
2.05
1.63
1.93
9.04
4.52
1.63
1.58
4.68
2.15

24.8
18.3
23.8
23.9
23.8
16.7
4.29
7.09
26.8
29.1
27.5
13.1
28.0
20.0
28.0
26.6
28.0
25.3
27.4
19.2
18.8
28.5
28.4
21.9
15.4

2.01
1.95
2.06
1.81
1.87
1.78
0.612
0.922
3.30
3.30
4.38
0.781
3.88
2.62
3.76
4.42
4.00
3.04
4.46
2.25
2.61
3.76
3.69
2.86
1.09

70.9
66.4
72.2
70.7
71.1
68.7
60.9
57.7
68.0
64.1
66.3
55.4
63.3
62.5
66.3
61.6
65.9
68.7
64.7
58.9
68.1
65.3
63.8
65.7
81.4

0.00911
5.06
0.00933
1.37
0.00911
3.78
14.4
11.5
0.0105
1.89
0.00986
14.2
1.72
7.27
0.0102
2.72
0.0106
1.35
1.02
8.52
4.98
0.0108
1.55
3.87
0.0113

2.85
3.63
3.03
2.96
2.99
4.12
14.2
8.14
2.54
2.21
2.41
4.24
2.27
3.13
2.36
2.31
2.35
2.72
2.36
3.06
3.62
2.29
2.25
3.00
5.30

C3S
C3S + C6AxFy
C3S
C3S
C3S
Grain boundary
C6AxFy
C6AxFy
C2S
C2S
C2S
Grain boundary
C2S
Grain boundary
C2S
Grain boundary
C2S
C2S + C
C2S
Grain boundary
Grain boundary
C2S
C2S
Grain boundary
Grain boundary

(Ca3 5xMn4xV0x)(Si1 2xP2x)O5 with x 0.005 (for inclusion less

than 0.69 wt.% Mn2O3). The X-ray analysis showed that the M3 polymorph of C3S was undoubtedly formed at Mn and P inclusions less
than 0.69 wt.%, Mn2O 3 and 0.62 wt.% P2 O 5. At higher amounts of
this order, the alite phase was not formed and solid solutions of C2S
take place with 2 CaOMnO2 and CaO compounds.
Recent work of Ifka et al. [17] has considered inorganic part of MBM
as raw materials. Calcium oxide (CaO) from apatite in bone meal has
been accounted in material balance as a potential reactant susceptible
to produce clinker phases. Indeed, by considering bone meal as raw
material, the content of limestone was adequately reduced and the content of P2O5 could climb from 1.11 wt.% without balancing to 1.52 wt.%.

The aim of the present investigation is to identify the composition of

clinker minerals as solid solutions with P2O5 after the addition of bone
meal (BM) ash to the basic raw mixture.

2. Experimental
2.1. The preparation of clinker samples
The ashes of BM, lime, marl and blast furnace slag with determined
chemical composition were used for preparation of the raw mixtures
(Table 1). Chemical analysis of starting raw materials was realized by

Table 5
EPMA line analysis of sample shown in Fig. 2.
Point

MgO
(wt.%)

Al2O3
(wt.%)

SiO2
(wt.%)

P2O5
(wt.%)

CaO
(wt.%)

Fe2O3
(wt.%)

CaO/SiO2

Solid solution

1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24

0.562
1.42
1.39
0.878
1.32
1.38
0.755
0.735
0.610
0.912
3.17
4.02
0.00129
0.00205
0.00164
0.00241
0.00260
0.00285
0.00293
0.927
0.00250
0.00246
0.356
0.00277

1.76
4.49
5.41
1.25
0.922
1.92
1.34
1.56
1.23
1.12
12.8
19.1
0.750
1.87
0.680
1.90
1.60
2.20
2.21
2.13
2.09
1.67
1.06
1.76

24.1
20.2
20.8
22.2
24.3
20.5
21.4
23.1
23.5
21.6
14.2
4.57
0.978
4.07
8.23
25.6
27.0
29.9
28.3
29.6
25.8
26.5
22.9
27.0

1.81
1.20
1.21
2.00
2.20
1.49
2.26
1.38
1.04
1.20
1.41
0.00302
0.00193
0.00287
1.26
4.51
4.22
2.88
3.94
3.43
4.33
3.89
3.44
4.50

71.7
67.7
68.3
73.7
71.3
74.7
74.3
73.2
73.6
74.0
58.6
55.7
69.2
90.9
87.9
68.0
65.0
63.8
65.6
63.9
65.3
66.8
72.2
65.3

0.00822
4.93
2.90
0.00867
0.00976
0.0101
0.00888
0.00927
0.00899
1.18
9.80
16.5
29.1
3.16
1.91
0.0112
2.10
1.19
0.0104
0.0111
2.49
1.20
0.0116
1.52

2.97
3.35
3.29
3.32
2.94
3.64
3.47
3.17
3.13
3.43
4.12
12.2
70.8
22.3
10.7
2.65
2.41
2.14
2.32
2.16
2.53
2.52
3.15
2.42

C3S
C3S + C6AxFy
C3S + C6AxFy
C3S
C3S
C3S
C3S
C3S
C3S
C3S
Grain boundary
C6AxFy
C2F + C
C
C
C2S + C
C2S
C2S
C2S
C2S
C2S
C2S
C2S + C
C2S

150

T. Ifka et al. / Cement and Concrete Research 59 (2014) 147154

X-Ray Fluorescence (XRF) Analysis Spectro 2000. The preparation of ash

is reported in [17].
Raw mixtures were prepared according to calculated recipe
(Table 2) and elected ash of BM additions. The value of lime saturation
factor (LSF) was kept below 100 at maximum ash of BM addition.
Two series of samples with different contents of the ash were
prepared.
1st series: The ash of BM was added to the basic mixtures without
computing its CaO into the total CaO needed to react with
SiO2, Al2O3 and Fe2O3. The lime saturation factor is higher
than that of mixture without ash addition.
2nd series: The CaO from the BM ash was considered in the calculation
of total CaO in the mixture. The lime saturation remains
constant, but the content of limestone decreases.
The homogeneous raw meals were pressed into pellets 3 g in weight
(11 MPa, pressure hold 2 min). The pellets were red at the temperature 1450 C. The rate of temperature increase was set to 10 C/min
and isothermal hold to 1 h. At this temperature, the samples were
taken out from furnace and cooled rapidly by air owing. Chemical
analysis of free lime (f-CaO) in the samples was achieved according to
ethylene glycol extraction method [18]. In order to identify clinker
minerals and to detect P2O5 content in their solid solutions, Electron
Probe Micro Analyzer (EPMA JEOL JXA-840A, EDS parameters
15 KV, Takeoff Angle 40.0) was used. All samples selected for microanalysis were carbon coated.
3. Results and discussion
3.1. Chemical analysis of free lime
The results of free lime analysis for both series of samples and
elected addition of BM ash to raw mixtures are shown in Table 3.
The free lime content increases with increasing ash of BM in both series of analyzed samples. The increase in f-CaO content in clinker is due
to the fact that P2O5 enters C2S and stabilizes it. Once P2O5 stabilizes C2S,
it becomes hard to react with CaO to form C3S. The increasing content
of P2O5 is the cause that the formation of alite is increasingly retarded
or later totally blocked. As it was mentioned by [19], P2O5 can be used
to stabilize -C2S against its transformation to -C2S. The comparison
of the free lime content in the 1st and 2nd series of samples burnt at
1450 C shows that the free lime content is lower in the 2nd series. It
means that considering CaO from the BM ash in the calculation of
total CaO in the mixture allows to burn a higher amount of MBM in
cement rotary kiln without negative inuence to clinker properties.

Fig. 2. Microstructure of the sample with 1.81 wt.%. P2O5 (1st series).

The f-CaO phase, present in the clinker with maximum P2O5

content mainly due to the stabilization of C2S, is located in the area of
points 1516 and 2022 (Fig. 3, Table 6).
The intervals of P2O5 content in alite and belite for both series of
samples are shown in Figs. 4 and 5. The P2O5 content in both phases increases with the content of P2O5 in the clinker. Figs. 4 and 5 present that
P2O5 content in belite is higher than that in alite. The content of P2O5 in
alite and belite is higher in the 2nd series. These results and the results
from chemical analysis of free lime (lower content of f-CaO in the 2nd
series of samples) showed that CaO in the form of calcium phosphate
is less reactive than CaO as product of limestone decomposition. CaO
as product of limestone decomposition reacts preferentially. Because
of the decreased addition of the limestone, CaO from calcium phosphate
is required to react with SiO2. This CaO and also P2O5 from calcium
phosphate enter the reaction to form belite with more P2O5 in its
structure.
3.3. The formulas of C2S and C3S solid solutions
The oxide composition obtained by the line analysis showed that in
addition to CaO and SiO2, alite and belite contain minor quantities of
MgO, Al2O3, P2O5 and Fe2O3 (Table 7). According to the quantities of

3.2. Chemical microanalysis results

The line analysis conducted by EPMA with detected oxide composition in each point in the line was done. C2S and C3S were identied
according to SiO2 content and CaO/SiO2 weight ratio.
As presented in Fig. 1, alite forms sharply bordered crystal (points 1
5). Belite crystals have mostly rounded shape (points 911, 13, 15, 1719,
2223). Oxide composition in points 7 and 8 which is located between
calcium silicate crystals showed the presence of C4AF in this area.
However, pure C4AF doesn't occur in the clinker. The compounds from
a variety of solid solutions between C2A and C2F are present. Therefore,
the more correct designation of aluminoferrite phase is C6AxFy
(Table 4).
Because cooling rate of the clinker is rapid, some calcium silicate
crystals have cracks. These cracks form as a result of thermal expansion
differences between alite or belite and interstitial phase (aluminate and
ferrite). As shown in Table 5, the content of P2O5 in C2F and C6AxFy is
minimal. The alite and belite accommodate nearly all the phosphorus
in the system.

Fig. 3. Microstructure of the sample with 1.81 wt.%. P2O5 (1st series).

T. Ifka et al. / Cement and Concrete Research 59 (2014) 147154

151

Table 6
EPMA line analysis of sample shown in Fig. 3.
Point

MgO
(wt.%)

Al2O3
(wt.%)

SiO2
(wt.%)

P2O5
(wt.%)

CaO
(wt.%)

Fe2O3
(wt.%)

CaO/SiO2

Solid solution

1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24

0.465
0.406
2.45
1.08
0.711
0.00159
0.00260
0.00275
0.537
0.542
0.449
0.350
0.782
0.748
1.22
1.23
0.00229
2.24
0.706
0.750
1.12
1.36
0.538
0.00251

1.90
1.91
12.8
4.23
1.71
1.59
2.05
2.50
3.73
2.29
2.19
1.98
2.40
5.45
0.00200
0.00251
1.34
9.47
6.37
0.00203
0.00187
0.695
3.25
2.16

26.9
26.8
4.98
18.3
26.7
15.5
28.0
29.2
26.6
27.8
26.2
14.8
20.6
15.7
0.00233
0.959
25.2
10.7
11.9
0.00256
0.00219
2.50
21.6
25.0

3.62
3.90
0.00249
2.03
4.42
1.28
4.71
4.56
3.92
3.55
3.23
1.54
2.41
2.26
0.00247
0.00288
3.47
0.643
1.21
0.00264
0.00223
0.00275
2.19
3.51

64.8
65.2
64.9
70.8
66.5
79.8
65.3
62.6
62.6
64.0
65.7
77.8
72.1
68.4
98.8
97.8
70.0
67.0
70.5
99.2
98.9
95.4
69.4
69.3

2.38
1.80
15.0
3.55
0.00996
1.86
0.00931
1.17
2.57
1.84
2.16
3.55
1.64
7.37
0.00757
0.00953
0.0108
9.88
9.26
0.00809
0.00754
0.00835
2.98
0.0104

2.41
2.43
13.0
3.88
2.49
5.15
2.33
2.14
2.35
2.30
2.51
5.27
3.50
4.35
42389.7
102.0
2.78
6.23
5.93
38799.3
45119.0
38.2
3.22
2.78

C2S
C2S
C6AxFy
C2S + C6AxFy
C2S
C2S + C
C2S
C2S
C2S
C2S
C2S
Grain boundary
C3S
Grain boundary
C
C
C2S + C
CxS + C6AxFy
CxS + C6AxFy
C
C
C
C3S
C2S + C

these oxides, the formulas of C2S and C3S solid solutions were calculated. For example, C3S solid solution (bolded in Table 7) formula from
line analysis shown in Fig. 6 is:
8

C2:951 M0:049 S0:936 A0:028 F0:007 P0:029

where C = CaO, M = MgO, S = SiO2, A = Al2O3, F = Fe2O3, and P =

P2O5.
Tables 811 contain nal formulas of C2S and C3S solid solutions
for all samples from both series. Each nal formula of solid solution
was calculated from 5 line analysis of the sample.
As shown in previous tables, the value of SiO2 stoichiometric coefcient decreases with increasing value of P2O5 stoichiometric coefcient
in belite and alite formulas. Decreasing value of SiO2 stoichiometric
coefcient is in accordance with ionic substitution stated in [11]. The
results also showed that PV enters the structure of C2S and C3S solid solutions with AlIII and FeIII. The values of Al2O3 and Fe2O3 stoichiometric
coefcients increase with increasing P2O5 stoichiometric coefcient in
the formulas of calcium silicate solid solutions. The comparison of the

C2S

Content of P2O5 in the phase (wt. %)

Content of P2O5 in the phase (wt. %)

C3S

0
0.0

values of Al2O3 and Fe2O3 stoichiometric coefcients in belite and alite

formulas showed that these calcium silicates incorporate more AlIII
than FeIII into their structures.
According to the dependences shown in Fig. 7, increasing content of
P2O5 added to the raw meal from ash of BM lowers the value of stoichiometric coefcient of SiO2 in both calcium silicate solid solutions.
The dependences in Figs. 8 and 9 present that the values of Al2O3
and Fe2O3 stoichiometric coefcients in solid solution formulas of both
calcium silicates in burnt clinker samples increase on the increasing
P2O5 addition from ash of BM to the raw meal.
Further increasing the addition of P2O5 to the raw meal will lead to
inability of belite and alite to incorporate more AlIII or FeIII into their
structures. The content of Al2O3 and Fe2O3 in calcium silicate solid
solutions should approach to some limit value.
Fig. 10 shows the dependences of P2O5 stoichiometric coefcient in
calcium silicate solid solution formulas on the content of P2O5 added
to the raw meal from ash of BM. The value of P2O5 stoichiometric
coefcient in both calcium silicate solid solutions increases with the
addition of P2O5 up to 1.9 wt.% to the raw meal. The comparison of the

0.4

0.8

1.2

1.6

P2O5 added from the ash of BM (wt. %)

Fig. 4. Content of P2O5 in belite and alite for the 1st series of samples.

2.0

C2S
C3S

0
0.0

0.4

0.8

1.2

1.6

P2O5 added from the ash of BM (wt. %)

Fig. 5. Content of P2O5 in belite and alite for the 2nd series of samples.

2.0

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T. Ifka et al. / Cement and Concrete Research 59 (2014) 147154

Table 7
EPMA line analysis of sample shown in Fig. 6. The values bolded were used to calculate the formula of C3S solid solutions.
Point

MgO
(wt.%)

Al2O3
(wt.%)

SiO2
(wt.%)

P2O5
(wt.%)

CaO
(wt.%)

Fe2O3
(wt.%)

CaO/SiO2

Solid solution

1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27

0.000569
0.000861
0.982
0.613
0.00199
0.886
0.745
4.27
0.00130
0.00214
1.09
0.801
1.07
0.965
1.00
0.793
4.07
0.655
1.63
0.648
1.73
1.91
0.924
0.643
0.502
2.01
0.501

0.000794
0.404
1.07
0.881
0.721
0.995
1.40
17.7
3.69
0.00258
0.00288
1.16
1.20
0.803
0.919
2.00
14.8
3.06
8.76
1.56
6.01
8.83
1.08
1.28
0.630
3.45
4.78

0.00176
1.18
22.2
18.4
14.6
20.9
22.8
3.91
1.90
19.7
21.9
21.5
22.3
22.6
23.7
24.1
10.6
25.5
8.69
22.4
1.19
14.3
22.5
22.6
18.8
17.0
3.10

0.00186
0.00217
1.61
0.00314
0.561
1.06
0.902
0.00322
0.00263
0.862
1.59
1.93
1.50
1.84
2.36
1.87
0.824
3.21
0.00307
2.08
0.639
0.00323
1.91
1.12
1.67
1.27
0.00268

81.4
88.8
74.2
80.1
84.1
76.1
73.2
56.3
74.1
79.5
75.4
74.6
72.5
72.8
70.2
71.3
58.2
65.5
67.2
73.3
86.5
70.3
73.6
74.4
78.4
74.2
77.5

18.6
9.67
0.00936
0.0101
0.00961
0.00949
1.01
17.9
20.3
0.0101
0.00934
0.00861
1.46
1.03
1.82
0.00902
11.5
2.06
13.7
0.00818
3.92
4.59
0.00881
0.00858
0.00943
2.07
14.1

46256.0
75.5
3.34
4.36
5.75
3.64
3.21
14.4
39.0
4.05
3.44
3.47
3.26
3.22
2.96
2.96
5.49
2.57
7.73
3.27
72.8
4.90
3.28
3.29
4.16
4.35
25.0

C2F + C
C2F + C
C3S
C3S + C
C3S + C
C3S
C3S
C6AxFy
C2F + C
C3S + C
C3S
C3S
C3S
C3S
C3S
C3S
Grain boundary
C2S
C6AxFy
C3S
C6AxFy
Grain boundary
C3S
C3S
C3S + C
Grain boundary
C6AxFy

values of P2O5 stoichiometric coefcients in belite and alite in both series of samples shows that more PV is incorporated in the structure of
calcium silicates in the 2nd series.
4. Conclusions

Fig. 6. Microstructure of the sample with 1.81 wt.%. P2O5 (1st series).

The electron microanalysis results showed that belite and alite

accommodate nearly all the phosphorus in the clinker. It was found out
that belite and alite contained more P2O5 in the samples where CaO
from ash of BM was considered in the calculation of total CaO in the
raw mixture. The formulas of C2S and C3S solid solutions were
computed from measured oxide composition. The increasing addition of
P2O5 to the basic raw mixture leads to decrease in SiO2 and increase in
P2O5, Al2O3 and Fe2O3 in both calcium silicate solid solutions. PV enters
the structure of calcium silicates with AlIII and FeIII. The content of Al2O3
in calcium silicates is higher than that of Fe2O3. It can be expected that
the quantity of SiO2, P2O5, Al2O3 and Fe2O3 in C2S and C3S solid solutions
will approach to some limit value (degree of saturation) with increasing
addition of P2O5 from the ash of BM. Searching for these limit values
doesn't have signicance in practical terms because the clinker will contain high content of free lime at higher addition of the BM ash.

Table 8
The formula of C2S solid solution in the 1st series of samples.
Addition of P2O5
(wt.%)

Solid solution formula of C2S

(C = CaO, M = MgO, S = SiO2, A = Al2O3, F = Fe2O3, P = P2O5)

0
0.38
0.75
1.11
1.46
1.81

C1.988 0.007 M0.012 0.007 S0.97518 0.00001 A0.019 0.001 F0.005 0.002P0.00005 0.00001
C1.988 0.002 M0.012 0.002 S0.957 0.004 A0.025 0.003 F0.009 0.004 P0.009 0.001
C1.987 0.007 M0.013 0.007 S0.940 0.007 A0.029 0.005 F0.009 0.004 P0.022 0.003
C1.987 0.005 M0.013 0.005 S0.924 0.004 A0.031 0.001 F0.011 0.002 P0.034 0.002
C1.987 0.002 M0.013 0.002 S0.909 0.004 A0.035 0.003 F0.011 0.003 P0.045 0.002
C1.987 0.006 M0.013 0.006 S0.897 0.005 A0.038 0.003 F0.012 0.003 P0.053 0.001

T. Ifka et al. / Cement and Concrete Research 59 (2014) 147154

153

Table 9
The formula of C3S solid solution in the 1st series of samples.
Addition of P2O5
(wt.%)

Solid solution formula of C3S

(C = CaO, M = MgO, S = SiO2, A = Al2O3, F = Fe2O3, P = P2O5)

0
0.38
0.75
1.11
1.46
1.81

C2.966 0.009 M0.034 0.009 S0.9922 0.0008 A0.0075 0.0008 F0.000170 0.000003 P0.0000595 0.0000009
C2.95 0.01 M0.05 0.01 S0.973 0.009 A0.016 0.002 F0.007 0.002 P0.0042 0.0001
C2.959 0.008 M0.041 0.008 S0.97 0.01 A0.0161 0.0005 F0.008 0.001 P0.011 0.004
C2.962 0.008 M0.038 0.008 S0.952 0.003 A0.022 0.004 F0.0081 0.0002 P0.018 0.003
C2.955 0.003 M0.045 0.003 S0.94 0.01 A0.027 0.001 F0.010 0.001 P0.0236 0.0032
C2.949 0.002 M0.051 0.002 S0.928 0.008 A0.031 0.003 F0.011 0.004 P0.030 0.001

Table 10
The formula of C2S solid solution in the 2nd series of samples.
Addition of P2O5
(wt.%)

Solid solution formula of C2S

(C = CaO, M = MgO, S = SiO2, A = Al2O3, F = Fe2O3, P = P2O5)

0
0.38
0.76
1.14
1.52
1.9

C1.988 0.007 M0.012 0.007 S0.97518 0.00001 A0.019 0.001 F0.005 0.002 P0.00005 0.00001
C1.988 0.002 M0.011 0.002 S0.936 0.005 A0.025 0.003 F0.012 0.003 P0.027 0.005
C1.982 0.007 M0.018 0.007 S0.926 0.007 A0.033 0.005 F0.013 0.003 P0.029 0.001
C1.984 0.005 M0.016 0.005 S0.911 0.001 A0.033 0.001 F0.013 0.002 P0.043 0.002
C1.97 0.02 M0.03 0.02 S0.894 0.006 A0.036 0.003 F0.014 0.004 P0.057 0.008
C1.987 0.002 M0.013 0.002 S0.886 0.004 A0.038 0.002 F0.016 0.003 P0.060 0.003

Table 11
The formula of C3S solid solution in the 2nd series of samples.
Addition of P2O5
(wt.%)

Solid solution formula of C3S

(C = CaO, M = MgO, S = SiO2, A = Al2O3, F = Fe2O3, P = P2O5)

0
0.38
0.76
1.14
1.52
1.9

C2.966 0.009 M0.034 0.009 S0.9922 0.0008 A0.0075 0.0008 F0.000170 0.000003 P0.0000595 0.0000009
C2.96 0.02 M0.04 0.02 S0.95 0.01 A0.022 0.003 F0.010 0.005 P0.015 0.006
C2.964 0.009 M0.036 0.009 S0.950 0.008 A0.023 0.004 F0.011 0.003 P0.016 0.004
C2.960 0.008 M0.030 0.008 S0.94 0.01 A0.025 0.003 F0.013 0.003 P0.026 0.009
C2.945 0.003 M0.055 0.003 S0.928 0.003 A0.031 0.002 F0.014 0.005 P0.028 0.004
C2.95 0.01 M0.05 0.01 S0.91 0.01 A0.033 0.007 F0.014 0.002 P0.040 0.007

Fig. 7. The dependence of SiO2 stoichiometric coefcient in the formula of belite and alite on the content of P2O5 added to the raw meal from ash of BM.

Fig. 8. The dependence of Al2O3 stoichiometric coefcient in the formula of belite and alite on the content of P2O5 added to the raw meal from ash of BM.

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T. Ifka et al. / Cement and Concrete Research 59 (2014) 147154

Fig. 9. The dependence of Fe2O3 stoichiometric coefcient in the formula of belite and alite on the content of P2O5 added to the raw meal from ash of BM.

Fig. 10. The dependence of P2O5 stoichiometric coefcient in the formula of belite and alite on the content of P2O5 added to the raw meal from ash of BM.

Acknowledgment
This work was supported by courtesy of the Slovak Grant Agency
(VEGA 1/0064/12) and by Project Centres for Materials Research at
FCH BUT, reg. no. CZ.1.05/2.1.00/01.0012.

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