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Departamento de Qumica Inorgnica, Cristalografa y Mineraloga, Universidad de Mlaga, 29071 Mlaga, Spain
Servicios Centrales de Investigacin, Universidad de Mlaga, 29071 Mlaga, Spain
a r t i c l e
i n f o
Article history:
Received 20 October 2011
Received in revised form 13 January 2012
Accepted 18 January 2012
Available online 1 February 2012
Keywords:
Rheology
Hydration
X-ray diffraction
Compressive strength
Cement paste
Sulfoaluminate
a b s t r a c t
Calcium sulfoaluminate (CSA) cements are currently receiving a lot of attention because their manufacture produces less CO2 than ordinary Portland cement (OPC). However, it is essential to understand all
parameters which may affect the hydration processes. This work deals with the study of the effect of several parameters, such as superplasticizer (SP), gypsum contents (10, 20 and 30 wt.%) and w/c ratio (0.4
and 0.5), on the properties of CSA pastes during early hydration. This characterization has been performed through rheological studies, Rietveld quantitative phase analysis of measured X-ray diffraction
patterns, thermal analysis and mercury porosimetry for pastes, and by compressive strength measurements for mortars. The effect of the used SP on the rheological properties has been established. Its addition makes little difference to the amount of ettringite formed but strongly decreases the large pore
fraction in the pastes. Furthermore, the SP role on compressive strength is variable, as it increases the values for mortars containing 30 wt.% gypsum but decreases the strengths for mortars containing 10 wt.%
gypsum.
2012 Elsevier Ltd. All rights reserved.
1. Introduction
Calcium sulfoaluminate (CSA) cements are receiving increasing
attention nowadays since their manufacture produces less CO2
than ordinary Portland cement (OPC) [14]. These binders may
have quite variable compositions, but all of them contain Yeelimite phase, also called Kleins salt or tetracalcium trialuminate sulfate (C4A3S) [5]. Cement nomenclature will be used hereafter
C = CaO, S = SiO2, A = Al2O3, F = Fe2O3, S = SO3, M = MgO, T = TiO2
and H = H2O. The term CSA cements is usually reserved for those
clinkers containing more than 50 wt.% of Kleins salt and they
may also have minor amount of phases such as C2S, CA, C4AF, CS,
CSH2, and so on [6]. Cements with large amounts of Yeelimite
may have special applications such as high strength developments
at early-ages [7,8] and radioactive element encapsulation in a
high-density cement paste [9,10]. On the other hand, a new related
type of cement is emerging, aimed to replace OPC in the long term
by combining approximately 2030 wt.% of Yeelimite (for earlyage strength development) and 5060 wt.% of activated belite
(for medium-age strength development) [1113]. This type of cement, initially developed in China but without the key activation
of belite, is known as sulfobelite and also as belite-calcium sulfoaluminate cement to stress the importance of belite in its composition and performance.
Al2O3
CaO
Fe2O3
K2O
SiO2
MgO
P2O5
TiO2
SO3
SrO
B2O3
Cr2O3
MnO
ZrO2
Na2O
CS10
Gypsum
33.80
41.80
2.37
0.25
8.20
2.73
0.13
1.50
8.80
0.15
0.02
0.01
0.07
<0.08
0.47
40.00
0.15
0.07
0.94
0.13
0.56
54.49
3.05
0.26
685
the ow curves of the cement pastes with 30, 20 and 10 wt.% gypsum
(Fig. 1ac, respectively) at a w/c ratio of 0.4 (CS10-X, w/c = 0.4) with
different SP contents. The insets show an enlarged view of the same
ow curves. In general, pastes (w/c = 0.4) without SP show a shear
thinning behavior and high viscosity values (between 2.6 and
3 Pa s at 50 s1). The addition of a small amount of additive, e.g.
0.1 wt.%, reduces drastically the viscosity of the pastes (0.2 Pa s
at 50 s1). From the viscosity curves (not shown), it can be observed
how deocculated pastes show a Newtonian behavior at shear rates
higher than 10 s1. Minimum viscosity values were obtained after
the addition of 0.15, 0.15 and 0.20 wt.% SP for CS10-30, CS10-20
and CS10-10, respectively, although the difference in viscosity is
not so remarkable. The gypsum content does not present an
important effect on the viscosity of the pastes in the studied range.
The selected SP amount for CS10-30, CS10-20 and CS10-10 pastes
with w/c = 0.5 was 0.15, 0.15 and 0.20 wt.% SP, respectively.
SP (wt%)
0.10
30
10
0
20
40
60
80
SP (wt%)
0.00
100
150
100
50
0
CS10-20
0.40
0.15, 0.20
20
20
40
60
80
100
0.10
0.40
0.15, 0.20
0.10
0.40
0.15, 0.20
20
10
0
20
40
60
80
SP (wt%)
0.00
100
150
100
0.10
0.40
0.15
50
0
20
40
60
80
100
-1
Shear Rate (s )
c
Shear Stress (Pa)
CS10-10
SP (wt%)
0.10
30
0.40
0.15
0.20
20
10
200
SP (wt%)
30
200
200
CS10-30
686
SP (wt%)
0.00
0
0
20
40
60
-1
80
100
Shear Rate (s )
150
100
50
0
0.10
0.15, 0.20, 0.40
0
20
40
60
80
100
687
Table 2
Direct RQPA results (wt.%) for anhydrous and hydrated (w/c = 0.4 and 0.5) CS10-30 cements (with and without superplasticizer). The numbers in parentheses are the standard
deviations.
Anhydrous
w/c = 0.4
t0
t3
t7
t28
t3
t7
C4A3S
33.4(2)
13.3(2)
10.4(2)
10.1(2)
15.0(2)
12.6(1)
9.3(2)
9.2(2)
CSH2
b-C2S
CaTiO3
MgO
AFt
ZnO
32.3(2)
12.4(2)
9.2(2)
9.4(2)
13.8(2)
12.5(1)
9.9(1)
13.7(2)
2.8(2)
1.3(1)
0.7(1)
2.0(2)
1.6(1)
0.9(1)
40.5(2)
29.3(1)
2.0(2)
1.5(1)
1.0(1)
47.6(2)
28.3(1)
1.7(2)
1.5(1)
0.9(1)
48.2(2)
28.2(1)
2.2(2)
1.6(1)
0.9(1)
36.1(3)
30.4(1)
2.3(2)
1.7(1)
1.0(1)
40.6(2)
29.3(1)
1.4(1)
1.3(1)
0.7(1)
50.3(2)
27.1(1)
2.3(2)
1.6(1)
1.0(1)
39.4(3)
32.8(1)
29.5(1)
w/c = 0.4, SP
w/c = 0.5, SP
t28
t7
Table 3
Direct RQPA results (wt.%) for anhydrous and hydrated (w/c 0.5) CS10-20 and CS10-10 cements after 0 days (anhydrous) and 7 days. The numbers in parentheses are the standard
deviations.
CS10-20
CS10-10
Anhydrous
t0
w/c = 0.4
t7
w/c = 0.4, SP
t7
w/c = 0.5, SP
t7
Anhydrous
t0
w/c = 0.4
t7
w/c = 0.4, SP
t7
w/c = 0.5, SP
t7
C4A3S
39.1(2)
19.5(2)
18.3(2)
CSH2
b-C2S
CaTiO3
MgO
AFt
ZnO
25.6(2)
7.3(2)
7.2(2)
15.4(2)
46.9(2)
22.6(3)
24.5(3)
20.4(3)
5.3(2)
15.3(2)
1.4(2)
1.1(1)
3.2(2)
1.9(2)
0.8(1)
29.4(1)
3.2(2)
2.0(1)
1.2(1)
34.0(3)
32.8(1)
2.7(2)
1.9(1)
1.1(1)
36.6(3)
32.2(1)
1.1(1)
2.8(2)
1.9(1)
1.2(1)
42.2(3)
31.2(1)
3.6(2)
2.3(1)
1.2(1)
30.7(1)
3.6(2)
2.3(1)
1.4(1)
33.4(3)
35.3(1)
3.7(2)
2.4(1)
1.4(1)
33.0(2)
33.9(1)
3.3(2)
2.3(1)
1.4(1)
36.9(2)
34.6(1)
ZnOty R
ZnOtx N
C4 A3 St y R C4 A3 St x N X
where ZnO(ty)R and C4A3S(ty)R are the (Rietveld-calculated) percentages of those phases at time ty. ZnO(tx)N and C4A3S(tx)N stand for
percentages of these phases at normalized tx, and X is the amount
of C4A3S that has reacted at time ty (tx < ty). X is used to infer the
amount of free water reacting and the amorphous phases formed
according to the chemical reactions. For example, to obtain normalized RQPA at t7 for CS10-30 pastes (w/c 0.5 and 0.15 wt.% SP) the
normalized RQPA at t0 (the previous time) is used. Thus, normalized
phase assemblage at t0 is: 24.3 wt.% of C4A3S, 23.5 wt.% of gypsum,
2.0 wt.% of b-C2S, 0.9 wt.% of CaTiO3, 0.5 wt.% of MgO, 21.4 wt.% of
ZnO and 27.3 wt.% of free water. Ettringite (AFt) is the only new
3
4
688
Fig. 2. Rietveld plot for anhydrous (a) and CS10-30 pastes (b). The latter contains
w/c = 0.5 and superplasticizer and was studied after 7 days of hydration.
Tables 4 and 5). The total water content for every paste, measured
by TG, is also shown in Tables 4 and 5 for comparison. The values
conrm that water is not lost in our experimental conditions.
Fig. 3 shows the evolution of normalized phase content data
(AFt and CSH2) for all the cement pastes after 7 days of hydration.
The results agree well as larger amounts of ettringite are measured
in samples with less amount of residual gypsum. In comparison to
ordinary Portland cement, CSA cements react faster and most of
the hydration heat occurs in the rst day of hydration [18]. Ettringite is the main crystalline hydration product together with amorphous aluminum hydroxide. If gypsum is depleted, then
monosulfate is formed according to Eq. (6). Furthermore, depending on the minor phases present in CSA cements, other hydration
products may occur such as CSH phases, strtlingite, katoite,
monocarboaluminate or hydrogarnet [38,39].
Table 4
Normalized data for CS10-30 pastes after 3, 7 and 28 hydration days. Theoretical total water, wth
T , and total water contents determined from TG are also shown.
w/c = 0.4
w/c = 0.4, SP
w/c = 0.5, SP
t0
t3
t7
t28
t0
t3
t7
t28
t0
C4A3S
33.6
14.9
11.7
11.2
33.6
16.8
14.2
10.1
30.9
10.1
CSH2
b-C2S
CaTiO3
MgO
Wf
AFt
Hydrated amorphous
32.4
13.8
10.4
10.5
32.4
15.6
14.1
10.9
29.9
15.1
2.8
1.3
29.9
2.3
1.7
9.8
45.5
12.0
TG, wT = 26.2
2.4
1.7
7.1
53.5
13.2
TG, wT = 28.6
2.0
1.8
6.6
54.0
13.9
TG, wT = 28.6
2.8
1.3
29.9
2.4
1.7
11.1
40.9
11.5
TG, wT = 26.3
2.6
1.9
9.2
45.6
12.4
TG, wT = 26.5
1.6
1.4
5.8
55.4
14.8
TG, wT = 28.6
2.5
1.2
0.6
34.9
2.6
1.8
1.1
11.8
43.3
14.2
TG, wT = 26.9
wth
T
23.1 for w/c = 0.4
27.3 for w/c = 0.5
t7
689
CS10-10
w/c = 0.4
w/c = 0.4, SP
w/c = 0.5, SP
w/c = 0.4
w/c = 0.4, SP
w/c = 0.5, SP
t0
t7
t0
t7
t0
t7
t0
t7
t0
t7
t0
t7
C4A3S
38.8
22.8
38.8
21.3
36.1
16.7
47.1
28.3
47.1
29.4
43.9
23.5
CSH2
b-C2S
CaTiO3
MgO
Wf
AFt
Hydrated amorphous
25.4
8.6
25.4
8.4
23.7
5.8
15.4
1.7
15.4
1.3
14.3
1.3
3.2
1.9
0.8
29.9
3.7
2.4
1.4
8.7
39.8
12.6
TG, wT = 21.2
3.2
1.9
0.8
29.9
3.2
2.2
1.2
7.4
42.7
13.6
TG, wT = 23.5
2.9
1.8
0.8
34.7
3.1
2.0
1.3
12.6
45.5
13.0
TG, wT = 26.4
3.7
2.4
1.2
30.2
4.5
2.9
1.7
2.4
41.9
16.6
TG, wT = 23.3
3.7
2.4
1.2
30.2
4.5
2.8
1.7
5.1
39.7
15.5
TG, wT = 21.3
3.4
2.2
1.2
35.0
3.8
2.7
1.7
8.5
42.3
16.2
TG, wT = 26.4
wth
T
23.1 for w/c = 0.4
27.3 for w/c = 0.5
Fig. 3. Normalized values for AFt and CSH2 for all the studied pastes after 7 days
hydration.
Fig. 5a shows that CS10-30 paste with w/c = 0.4 and without SP
shows a bimodal behavior with pores centered at 12 and 554 nm
(see also Table 6). Higher amounts of water (w/c = 0.5) enlarge
the average size of the pores to 21 and 677 nm, as expected. This
bimodal behavior has been previously reported for CSA pastes
[19]. The addition of SP slightly enlarges the small pore diameters
(see Fig. 5a and Table 6) but strongly decreases the amount of the
large pores (those with diameters close to 500 nm or larger).
CS10-20 and CS10-10 pastes present the same tendency in the
pore size and pore size distribution. The increase in w/c ratio increases the size of the pores. Furthermore, the addition of superplasticizers strongly decreases (removes) the large pores and
slightly increases the size of the nanometer-pores (see Table 6
and Fig. 5b and c).
Table 6 also reports the total open porosity for the studied
pastes. As expected, the total open porosity increases with the w/
c ratio (for a given gypsum content). Moreover the addition of a
small amount of SP decreases the pastes open porosity for the
studied w/c ratios. Therefore, SP addition may increase the durability and mechanical strength of the mortars as the reduction of
porosity is a key for obtaining these objectives. Finally, Table 6 also
shows the corresponding values for an OPC paste (w/c = 0.4) for the
sake of comparison. The obtained values for OPC are in agreement
with those previously reported in the literature [40].
3.5. Compressive strength measurements
Fig. 4. DTA-TGA curves for CS10-30 (a) and CS10-10 (b) pastes after 7 days
hydration.
690
Fig. 5. Average pore diameter of the studied ceramic pastes. The insets show enlarged views of the large pore region.
Table 6
Percentage of porosity and average pore diameters for the studied pastes (7 days of
hydration).
SP
SP
SP
SP
SP
SP
Open
porosity
(vol.%)
Average small
pore diameter (nm)
12.0
11.5
14.8
14.4
15.6
13.7
15.8
10.8
14.1
13.3
13.6
9.9
9.6
12
12
21
11
17
12
17
26
50
17
40
17
26
Table 7
Compressive strength for CS10 mortar (cubes of 30 30 30 mm dimensions) at
different hydration ages. The numbers in parentheses are the standard deviations.
Average large
pore diameter (nm)
350
554
677
676
829
678
1329
SP
SP
SP
SP
SP
SP
41.5(0.6)
32.9(0.9)
32.2(0.2)
44.0(1.1)
36.7(0.3)
43.1(0.2)
34.5(0.4)
36.7(1.2)
33.3(0.2)
44.9(0.2)
36.1(0.4)
38.1(0.8)
34.9(0.6)
50.6(0.7)
40.6(1.0)
37.6(0.6)
47.5(1.4)
40.9(0.9)
50.0(0.6)
35.1(1.2)
45.6(0.5)
39.2(0.8)
46.1(0.9)
37.0(0.5)
39.3(0.9)
35.1(0.4)
691