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Scientific paper
Abstract
The X-ray diffraction (XRD)/Rietveld method was applied to analyze the hydration progress of cement paste prepared
with blast furnace slag powder (BFS) and limestone powder (LSP). The Rietveld method can be used to quantify the
amount of amorphous phase as well as crystalline phases. However, in cement paste containing BFS, two kinds of
amorphous phases, unhydrated BFS and C-S-H, are included and the Rietveld method cannot distinguish them. In order to
discriminate these two phases, a selective dissolution method was used to quantify the amount of unhydrated BFS. By
combining these two methods, it became possible to quantify the amount of BFS and C-S-H in hydrated cement. The
analysis results show that BFS accelerates the hydration of C3S, C3A, and especially C4AF. The strength increasing effect
of LSP is more pronounced in the ordinary Portland cement (OPC) BFS system than in the OPC system. This is attributed to the higher amount of calcium aluminate hydrates generated in the BFS contained system compared to the
system without BFS. The additional calcium aluminate hydrates fill pores as calcium carboxaluminate by the reaction
with LSP, increasing the compressive strength. These results show the effectiveness of the XRD/Rietveld method as an
analysis tool for cement hydration relating to various properties of cement materials.
1. Introduction
The X-ray diffraction (XRD)/Rietveld method has been
used and applied for the quantification of crystalline
phases such as cement minerals. Recently, it has also
been applied for the quantitative analysis of cement
phases containing various mineral admixtures (Hoshino
et al. 2005) and hydration analysis of cement paste
(Scrivener et al. 2004, Hoshino et al. 2006). One characteristic point of these recent applications is the quantification of amorphous phases.
In most previous studies of hydration analysis using
the Rietveld method, the materials analyzed consisted
mainly of pure cement or cement containing a crystalline
mineral admixture such as limestone powder (LSP) but
were very limited for cement containing amorphous
phases such as blast furnace slag powder (BFS). In general, the quantification of amorphous phases by the
Rietveld method is done by the addition of a specific
amount of internal standard such as corundum (Al2O3).
The quantified amount of corundum is greater than the
amount added when the sample contains an amorphous
phase, and the amount of amorphous phase is estimated
from this measured value (Jones et al. 2000). The estimated value is the total amount of amorphous phases.
Therefore, when the sample contains more than two
phases of amorphous materials, it is generally impossible
to estimate the amount of each amorphous phase by this
1
method.
When cement paste contains BFS, two kinds of
amorphous phases are considered to exist. One of them is
C-S-H generated by the hydration of cement and BFS,
and the other is the unhydrated BFS. Both phases show a
diffraction halo at a similar position around 2 = 31
(CuK) in XRD profiles. Therefore, it is difficult to
distinguish these two phases only by the Rietveld method
and the hydration analysis of BFS blended cement requires advanced techniques such as ones that combine
multiple methods. As for the quantitativity of the Rietveld method, the accuracy of quantification has to be
verified for every phase separately through comparison
with other reliable methods because of the large number
of adjustable parameters and several factors not usually
considered such as solid solution, polymorphism, and
differences in X-ray adsorption depending on chemical
composition.
Regarding the hydration reaction of BFS blended
cement, some studies have reported about the hydration
process of individual cement minerals. BFS is reported to
accelerate the hydration of C3S (Ogawa et al. 1980,
Uchikawa 1986, Imoto et al. 2001), to delay the hydration of C3A estimated from the analysis of C3A-mellilite
glass system (Hanada and Ito 1969), and to delay the
hydration of C4AF at an early age estimated from the
analysis of the C4AF-BFS system (Asaga and Kuga
1996). However, studies on the hydration analysis of
BFS blended cement have been very limited. One objective of this study is the establishment of a method to
quantify BFS blended cement hydration.
Another objective of this study is the investigation of
the mechanism of LSP influence on the strength of cement paste. The effect of LSP on the hydration of C3S has
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S. Hoshino, K. Yamada and H. Hirao / Journal of Advanced Concrete Technology Vol. 4, No. 3, 357-367, 2006
been reported (Ramachandran 1986), as has the interaction between calcium aluminate phase and LSP (Jambor
1980). Based on these studies, the hydration of BFS
blended cement containing LSP was analyzed in this
study. It has been reported that LSP increases the strength
of cement and that this effect is especially significant in
the system of BFS blended cement (Shimobayashi et al.
1979). Although this kind of phenomena has been reported, the mechanism of this strength increase is not
known and there are no studies from the standpoint of
hydration analysis to the authors knowledge.
Based on this background, a combined
XRD/Rietveld-selective dissolution method was adopted
to quantify the hydration of cement containing BFS and
LSP. The measurement results were used to estimate the
mechanism of strength development. Through this investigation, the authors tried to show the effectiveness of
this combined analytical method for the properties of
cement based materials.
2. Experiments
2.1 Sample preparation
The materials used in this study were ordinary Portland
cement (OPC), BFS, and LSP with 3250 cm2/g, 4480
cm2/g, and 5270 cm2/g of Blaine specific surface area,
respectively. The chemical compositions of OPC and
BFS are shown in Table 1. The mineral composition of
OPC is shown in Table 2. The mix proportions of the
cement and additives prepared in this study are shown in
Table 3. Four kinds of blend were examined, OPC, OPC
with 4 mass% of LSP by substitution, OPC replaced by
40 mass% BFS, and 40 mass% BFS-OPC with 4 mass%
of LSP by substitution.
Cement paste with a water-to-cement ratio of 0.50 was
mixed in a Hobart mixer for 3 min. The mixed paste was
kept in a sealed container at 20C for 3, 7, and 28 days. At
each age, hydration was stopped by immersion into
acetone and the specimen was kept under RH11% for 7
days before being used for analysis.
2.2 Measurements
(1) Thermal gravity and differential thermal
analysis (TG-DTA)
Calcium hydrate (CH) and ignition loss (1000C, ig.loss)
was quantified by using TG-DTA. In the analysis done in
this study, the value was calibrated to eliminate the effects of mass loss by the decarbonation of calcite and the
dehydration of gypsum.
C3 S
59.6
C2 S
12.6
C3 A
6.8
C4AF
14.1
Gypsum
4.0
OPC-LSP
100
4
OPC-BFS
60
40
OPC-BFS-LSP 60
40
4
Sample Name
OPC
BFS
SO3
3.02
2.01
Na2O
0.36
0.21
K2O
0.40
0.41
TiO2
0.37
0.56
P2O5
0.42
0.02
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S. Hoshino, K. Yamada and H. Hirao / Journal of Advanced Concrete Technology Vol. 4, No. 3, 357-367, 2006
100
Intensity
(1)
OPC Minerals
Ca(OH)2
Ettringilte
Monosulfate
Corundum (internal standard)
10
20
30
2()
40
50
60
Intensity
100 ( A R )
A ( 100 R )
OPC Minerals
Calcite
Ca(OH)2
Ettringite
Monocarbonate
Hemicarbonate
Corundum Internal Standard
10
20
30
40
50
60
2()
Intensity
G=
OPC Minerals
Ca(OH)2
Ettringilte
Monosulfate
Corundum (internal standard)
10
20
30
2()
40
50
60
Intensity
OPC Minerals
Calcite
Ca(OH)2
Ettringite
Monocarbonate
Hemicarbonate
Corundum Internal Standard
10
20
30
2()
40
50
60
S. Hoshino, K. Yamada and H. Hirao / Journal of Advanced Concrete Technology Vol. 4, No. 3, 357-367, 2006
80
60
40
OPC
OPC-LSP
OPC-BFS
OPC-BFS-LSP
20
0
10
20
Age (days)
30
100
80
60
40
OPC
OPC-LSP
OPC-BFS
OPC-BFS-LSP
20
0
10
20
Age (days)
30
80
80
Reaction Ratio of BFS (%)
100
OPC-BFS
OPC-BFS-LSP
60
60
40
40
20
20
10
20
Age (days)
0
30
360
silicates.
The relationship between the reaction amount of cal-
361
OPS
OPC-LSP
OPC-BFS
OPC-BFS-LSP
80
Production Amount of C-S-H (%)
60
40
OPC
OPC-LSP
OPC-BFS
OPC-BFS-LSP
10
20
Age (days)
40
20
[Production Amount of C-S-H in Pastes without BFS]
0.991[Reaction Amount of Calcium Silicate ]
R 2 0.996
0
0
30
cium silicates, which is the sum of C3S and C2S, and the
produced amount of C-S-H, is shown in Fig. 6. In the
cases of OPC and OPC-LSP, the produced amount of
C-S-H increases proportionally with increases in the
reaction amount of calcium silicate following a linear
line that crosses the origin. In this study, the amounts of
calcium silicates and amorphous phase were quantified
simultaneously by the Rietveld method. This method
gave a good correlation between the reaction amount of
calcium silicate and the produced amount of C-S-H.
Thus the accuracy of this method can be judged high
enough to warrant further investigation.
In the cases containing BFS of OPC-BFS and
OPC-BFS-LSP, the amounts of C-S-H produced for the
same reaction amount of calcium silicates were greater
than in the cases of OPC and OPC-LSP. This is caused by
the formation of C-S-H from BFS and the difference
between the two systems represents the produced amount
of C-S-H from BFS.
Based on this discussion, the development of the total
amount of C-S-H and C-S-H produced from calcium
silicates in the case of OPC-BFS is shown in Fig. 7. In
this result, the difference between the amount of C-S-H
from the total and that from calcium silicates is assumed
as the produced amount of C-S-H from BFS. The amount
of C-S-H from calcium silicates increases rapidly until
the age of 3 days and then rises at a slower rate until the
age of 28 days. On the other hand, although the amount
of C-S-H from BFS is limited at the age of 3 days and the
ratio to the total amount of C-S-H is low, the produced
amount increases with age and the ratio becomes significant at the age of 28 days.
The relationship between the total reaction amount of
calcium silicates and BFS and the produced amount of
C-S-H are shown in Fig. 8. There is a linear correlation
crossing the origin, which indicates that similar amounts
of C-S-H are produced from the same amounts of calcium silicates and BFS.
20
40
60
80
Production Amount of C-S-H (%)
20
60
OPC-BFS
Total Amounut of C-S-H
C-S-H Produced from
Calcium Silicates
60
Amount
C-S-H Produced from BFS
40
20
C-S-H Produced
from Calcium Silicate
10
20
Age (days)
30
80
Production Amount of C-S-H (%)
S. Hoshino, K. Yamada and H. Hirao / Journal of Advanced Concrete Technology Vol. 4, No. 3, 357-367, 2006
60
OPS
OPC-LSP
OPC-BFS
OPC-BFS-LSP
40
20
0
0
20
40
60
80
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S. Hoshino, K. Yamada and H. Hirao / Journal of Advanced Concrete Technology Vol. 4, No. 3, 357-367, 2006
20
15
10
5
0
0
10
20
Age (days)
Age
Ca/Si molar ratio
3d
7d
28d
1.98
1.92
1.83
OPC
OPC-LSP
OPC-BFS
OPC-BFS-LSP
25
30
100
20
OPC
OPC-LSP
OPC-BFS
OPC-BFS-LSP
25
15
10
5
0
0
10
15
20
25
80
60
40
OPC
OPC-LSP
OPC-BFS
OPC-BFS-LSP
20
0
10
20
Age (days)
30
363
S. Hoshino, K. Yamada and H. Hirao / Journal of Advanced Concrete Technology Vol. 4, No. 3, 357-367, 2006
100
OPC
OPC-LSP
OPC-BFS
OPC-BFS-LSP
80
60
40
20
0
10 15 20
Age (days)
25
30
OPC
20
C3A
Gypsum
Ettringite
Monosulfate
20
retarded by melilite glass (Hanada and Ito 1969). Regarding the hydration of C4AF, based on the measurement of hydration heat development of the
C4AF-BFS-Gypsum system, BFS was reported to delay
the hydration of C4AF (Asaga and Kuga 1996). However,
in this study on C3A and C4AF, after the age of 3 days,
hydration of both phases was accelerated by BFS. More
accurate evaluation of these contradicting results is
needed.
The hydration reactions of the calcium aluminate
phases of OPC, OPC-LSP, OPC-BFS, and
OPC-LSP-BFS are shown in Fig. 13. The quantification
errors of these phases were confirmed to be less than 1.2
mass% in a separate study (Hoshino et al. 2006).
In the case of OPC, the amounts of C3A and gypsum
decreased and the amount of Ms increased with age. The
amount of Ett showed a peak at the age of 3 days. In the
case of OPC-LSP, although Ett formation at early ages
was the same as in the case of OPC, later hydration became different, with Ett not transforming into Ms but
remaining a constant amount from 3 to 28 days, while
Mc and Hc were produced and their amounts increased
15
10
10
20
Age (days)
15
Ettringite
Monosulfate
Monocarbonate
Hemicarbonate
10
30
OPC-BFS
20
Ettringite
Monosulfate
C 3A
Gypsum
C3A
Gypsum
LSP
20
OPC-LSP
15
10
10
20
Age (days)
30
OPC-BFS-LSP
C 3A
Gypsum
LSP
15
Ettringite
Monosulfate
Monocarbonate
Hemicarbonate
10
0
0
10
20
Age (days)
30
10
20
Age (days)
30
40
OPC
OPC-LSP
OPC-BFS
OPC-BFS-LSP
20
0
10
20
Age (days)
30
30
25
20
15
10
OPC
OPC-LSP
OPC-BFS
OPC-BFS-LSP
5
0
0
20
40
60
80
100
60
40
OPC-BFS-LSP
20
OPC-BFS
60
OPC-LSP
80
OPC
100
ig.loss (%)
S. Hoshino, K. Yamada and H. Hirao / Journal of Advanced Concrete Technology Vol. 4, No. 3, 357-367, 2006
364
28days
7days
3days
365
S. Hoshino, K. Yamada and H. Hirao / Journal of Advanced Concrete Technology Vol. 4, No. 3, 357-367, 2006
Phase
OPC
LSP
C-S-H
CH
Ett
Ms
Mc
Hc
Density
(g/cm3)
3.15
2.72
1.90
2.24
1.78
2.01
2.17
1.98
OPC
0d
OPC
3d
Ms
C-S-H
CH Ett
7d
28d
0d
OPC-LSP
LSP
OPC
3d
C-S-H
Mc Hc
CH Ett
7d
28d
0d
OPC-BFS
OPC-BFS-LSP
OPC
3d
BFS
C-S-H
Ms
CH Ett
7d
28d
0d
OPC
3d
BFS
C-S-H
LSP
CH Ett
7d
28d
Mc Hc
20
40
60
Theoretical Volume Occupancy (Vol%)
S. Hoshino, K. Yamada and H. Hirao / Journal of Advanced Concrete Technology Vol. 4, No. 3, 357-367, 2006
60
OPC
OPC-LSP
OPC-BFS
OPC-BFS-LSP
55
48
46
44
42
40
38
0 3
Age (days)
28
5. Conclusions
The analysis of hydration reaction of cement paste containing BFS and LSP by applying the XRD/Rietveld
method was investigated.
(1) By the combination of the Rietveld method and
selective dissolution method, the hydration reaction
of cement containing two amorphous phases of
C-S-H and unreacted BFS was successfully quantified.
(2) By the addition of BFS, after the age of 3 days, every
major phase such as C3S, C2S, C3A, and C4AF in
cement was accelerated to hydrate. The acceleration
was most significant for C4AF.
(3) By the addition of LSP, carboaluminate hydrates
such as monocarbonate and hemicarbonate were
generated. The produced amount of carboaluminate
was greater when BFS was added.
366
60
OPC
OPC-LSP
OPC-BFS
OPC-BFS-LSP
40
20
0
36 38 40 42 44 46 48 50
Theoretical Porosity by Rietveld Method (%)
S. Hoshino, K. Yamada and H. Hirao / Journal of Advanced Concrete Technology Vol. 4, No. 3, 357-367, 2006
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