Advances in Cement Research Advances in Cement Research

http://dx.doi.org/10.1680/jadcr.16.00112
Paper 1600112
Active sulfate-rich belite Received 22/08/2016; revised 13/12/2016; accepted 23/12/2016
sulfoaluminate cement Keywords: boron, borates/C2S/compressive strength

Shen, Yang, Zhang and Qian ICE Publishing: All rights reserved

Active sulfate-rich belite

sulfoaluminate cement
Yan Shen Ming Zhang
Lecturer, College of Civil Science and Engineering, Yangzhou University, Lecturer, College of Civil Science and Engineering, Yangzhou University,
Yangzhou, P. R. China (corresponding author: [email protected]) Yangzhou, P. R. China
Dingyi Yang Jueshi Qian
Professor, College of Civil Science and Engineering, Yangzhou University, Professor, College of Material Science and Engineering, Chongqing
Yangzhou, P. R. China University, Chongqing, P. R. China

This work focuses on the activation of belite to improve the strength development of sulfate-rich belite
sulfoaluminate cements. Borax was used to act as an activator to promote stabilisation of high-temperature belite
polymorphs. The phase compositions of clinkers were analysed by using quantitative X-ray powder diffraction. The
transformation of β-belite (C2S) to α′-C2S mainly depends on the dosage of borax, and the change in polymorphs is
almost complete when the dosage of borax reaches 5%. The formation of α′-C2S can significantly increase the
compressive strength and the concentration of borax has a great effect on the strength development of the activated
cements. The hydration products of activated cements were also investigated. The results show that the activation of
belite can promote the formation of ettringite. Moreover, the crystallisation of ettringite is also affected by the
polymorphs of belite, and a fine microstructure of ettringite is found in the activated cement paste.

Introduction only compensates for sulfur emissions, but also causes the
The pressure to reduce energy consumption and carbon dioxide anhydrite phase to remain in the produced clinkers. This for-
(CO2) emissions during ordinary Portland cement (OPC) mulation corresponds to sulfate-rich BSA clinkers, with belite,
manufacture has been one of the factors contributing to the ye’elimite, ferrite and anhydrite as the main phases (Shen and
development of novel cements (Quillin, 2001). Cements based Qian, 2015). The formulation relies on the equilibrium system
on belite have been proposed as environmentally friendly build- C2S–C4A3Ŝ–C4AF–CŜ where the anhydrite phase is in the
ing materials, as the reduction of carbon dioxide emissions may range of 0–20%.
be as much as 10% for belite Portland cements (Chatterjee,
1996; Guerrero et al., 2004) or up to 35% in belite calcium sul- BSA cements generally give high mechanical strength at early
foaluminate (BSA) cements (Cuberos et al., 2010; Quillin, ages due to the high reactivity of calcium sulfoaluminate phase,
2007). Furthermore, the sintering temperature of calcium sulfo- but later strength development after 28 d is slow (Cuberos et al.,
aluminate is 100–150°C lower than that of the calcium silicate 2010). The low mechanical strengths at later ages can be
in OPC (Ma et al., 2014). Thus, BSA cements hold promise for ascribed to the slow hydration rate of the belite phase. This
reduced energy consumption and carbon dioxide emissions. In drawback can be overcome by stabilising hydraulically active
BSA cements, belite is an important mineral phase in addition forms of belite, specifically related to high-temperature modi-
to calcium sulfoaluminate and the most common formulation fications (Staněk and Sulovský, 2015). Stoichiometric C2S
of BSA cements is belite (C2S), ye’elimite (C4A3Ŝ) and ferrite has five polymorphs: α (hexagonal), αH′ (orthorhombic), αL′
(C4AF). BSA cements are characterised by rapid hardening, (orthorhombic), β (monoclinic) and γ (orthorhombic) (Ghosh
excellent durability and adjustability of expansibility. et al., 1979). Polymorphic transformations of belite, which
occur during cooling from temperatures above 1400°C, are
Usually BSA clinkers can be made from natural gypsum demonstrated by the scheme (Figure 1). The stabilisation of
(NG), limestone and bauxite. Because the solid industrial each form depends on the kind and amount of dopants em-
byproducts, such as alumina-containing fly ash, red mud and ployed, the burning temperature and the cooling rate. Typically,
desulfurisation gypsum (FGD), can be used to replace bauxite the main polymorph of belite in industrial BSA clinkers is the
and gypsum (Arjunan et al., 1999; Gartner, 2004; Pace et al., β phase. The β form is a metastable phase at room temperature
2011; Sahu and Majling, 1994), material resources are avail- and can be stabilised against the transformation to the γ phase
able to produce BSA clinkers. However, a small amount of by doping (Staněk and Sulovský, 2012). It has been shown that
gypsum inevitably decomposes at temperatures above 1200°C, certain minor oxides, such as magnesium oxide (MgO), dipho-
which can result in a shortage of gypsum and affect the for- sphorus pentoxide (P2O5), potassium oxide (K2O), barium
mation of ye’elimite (Wu et al., 2011). Therefore, an excess oxide (BaO) and sulfur trioxide (SO3), promote the formation
of gypsum should be added to raw materials to promote of α′-C2S and increase its hydraulic properties (Bensted, 1979;
the formation of ye’elimite (Marroccoli et al., 2010). In this Fukuda et al., 2001). Boron trioxide (B2O3) can also help to
work, phosphogypsum (PG) is used for the production of BSA stabilise high-temperature polymorphs of C2S (Jelenic et al.,
cements and excessive PG is added to raw materials, which not 1978). Recently, a new class of belite calcium sulfoaluminate

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 Advances in Cement Research Active sulfate-rich belite
sulfoaluminate cement
Shen, Yang, Zhang and Qian

1420°C 1160°C 670°C < 500°C

α α'H α'L β γ

780~860°C

Figure 1. Polymorphic phase transitions of belite with temperature

ferrite cement has been proposed by Lafarge (Li and Gartner, Table 1. Chemical composition of raw materials used for cement
2006; Walenta et al., 2010, 2011) in which stabilisation of high- clinkers (wt%)
temperature belite polymorphs (α′-forms) has been promoted Oxide Limestone Bauxite PG
(for instance with borax) to enhance later strength development
Calcium oxide (CaO) 44·79 0·20 31·04
of these cements. Moreover, previous studies reported that borax
Silicon dioxide (SiO2) 8·75 19·78 9·10
facilitates the formation of α′-C2S and enables increased Aluminium oxide (Al2O3) 2·71 51·73 0·46
addition of fly ash as the supplementary component in high- Iron (III) oxide (Fe2O3) 1·59 8·94 0·17
belite sulfoaliuminate cement (Ma et al., 2014). Magnesium oxide (MgO) 1·26 0·30 0·03
Diphosphorus pentoxide (P2O5) 0·05 0·10 0·69
Sulfur trioxide (SO3) 0·26 0·16 39·02
The objective of this study is to investigate the activation of
Loss on ignition (LOI) 38·60 12·38 18·50
belite with borax in sulfate-rich BSA cements. The influence of
the concentration of borax on the formation of α′-C2S and the
final properties of the resulting cements are studied. The
hydration behaviour of the active sulfate-rich BSA cements is Table 2. Phase compositions of sulfate-rich BSA clinkers (wt%)
also discussed to better understand the effect of the transform- Clinker C2S C4A3Ŝ C4AF CŜ
ation of belite polymorph from β to α′. The driving force for
C1 45 35 10 10
this research is the need to manufacture, and to understand the C2 30 40 10 20
production of, highly reactive BSA cements.

Experimental work iron from raw materials are not sufficient. Borax was added to
the mixtures (2%, 3%, 4% and 5% wt% of Na2B4O7·10H2O)
Materials
to promote room temperature stabilisation of the reactive belite
The raw materials used in the preparation of sulfate-rich BSA
polymorph. The proportioned raw materials were mixed with
clinkers were limestone, low-grade bauxite and PG. Limestone
water and pressed into a disc mould (50 mm dia.  8 mm).
and bauxite were obtained from the market in Chongqing,
The discs were dried in an oven at 100°C for 2 h and clinkered
China. The sample of PG was obtained from a phosphate ferti-
in 250 g batches in porcelain crucibles in a silicon–
liser plant in Yun Nan, China. The clinkers were activated by
molybdenum (Si–Mo) rod resistance furnace. First, the discs
adding borax (99% Na2B4O7·10H2O) to the raw material. The
were fired at 850°C for 30 min after ramping up at a heating
chemical compositions of the raw materials are given in Table 1.
rate of 5°C/min. Then, the temperature was raised at the same
All the materials were dried in an oven to constant weight, and
rate to 1270°C and held for 30 min. Finally, the clinkers were
then ground to pass through a 200-mesh sieve. In addition, the
removed from the furnace and rapidly cooled with forced air.
analytical grade chemicals used for the synthesis of clinkers
The BSA clinkers so prepared were ground in a laboratory ball
were aluminium oxide (Al2O3) and iron (III) oxide (Fe2O3) with
mill to reach the target Blaine surface area of 350 m2/kg.
>99% purity; these were provided by Bayer (Shanghai, China).

Synthesis of active sulfate-rich BSA clinkers Testing methods

In this study, two clinkers with varied proportions of ye’elimite Cement paste specimens for compressive strength tests were
and anhydrite were synthesised. The intended mineralogical prepared at a water to cement (w/c) ratio of 0·5, and the size
compositions of the two clinkers are shown in Table 2. The was 20 mm  20 mm  20 mm. All the specimens were cured
raw mix proportion of limestone, bauxite and PG was deter- at 20 ± 1°C and 95% relative humidity. After 24 h of mould-
mined according to a modified Bogue calculation (Shen and curing at 20°C, the samples were demoulded and cured in
Qian, 2015). Table 3 gives the mix proportions of the raw water at 20°C until measurements were performed. The com-
materials. In the two mixtures, pure aluminium oxide and iron pressive strengths were tested at ages of 7, 28 and 56 d.
(III) oxide were added to the raw meal as additional alumina Six samples were tested for each curing time, the average of
and iron providers because the provision of alumina and which was taken to be the representative strength value.

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 Advances in Cement Research Active sulfate-rich belite
sulfoaluminate cement
Shen, Yang, Zhang and Qian

Table 3. The proportions of raw materials (wt%)

Mixture Limestone Bauxite PG Aluminium oxide (Al2O3) Iron (III) oxide (Fe2O3)

C1 62·2 17·3 16·0 3·8 0·7

C2 56·2 10·9 24·3 6·5 2·1

The hydration of the samples at different curing ages was 1 –

1 C4A3S 2 β-C2S
stopped by submerging a part of the crushed samples into
3 α'-C2S 4 C4AF
ethanol for 2 d, and then the samples were dried in a vacuum –
4 5 CS
desiccator and ground to pass through a 0·08 mm sieve prior
to analysis. 1
3
1
The mineral compositions of the synthetic clinkers and the 5% 1
hydration samples were analysed with X-ray diffraction (XRD)
3
on a Bruker D8 Advance X-ray diffractometer (voltage 40 kV, 4%
electric current 40 mA, copper target). The quantitative ana-
lysis of minerals was conducted using Rietveld refinement 3%
performed with Topas 4.2 software. The microstructures of
the samples were observed by scanning electron microscopy 3
2%
(SEM) (Tescan Vega 3). The samples were metallised by gold
2
sputtering to promote electrical conductivity. The hydration 0% 1 2
5 22
heat release of the cements was tested by a Tam Air isothermal
calorimeter, and the cement pastes (w/c ratio of 0·5) were 10 20 30 40 50 60
mixed before testing. 2θ: degrees
(a)
Results and discussion –
1 C4A3S 2 β-C2S
Clinkering of active sulfate-rich BSA clinkers 3 α'-C2S 4 C4AF
The XRD analysis of the synthetic sulfate-rich BSA clinkers –
5 CS
clearly shows the mineralogical composition, as presented 4
in Figure 2. It can be clearly seen that the main crystalline 1
5 1
phases in the inactive sulfate-rich BSA clinker are ye’elimite,
3 1
belite, ferrite and anhydrite. Peaks of free lime were not found 5% 1
in any of the clinkers and the content of free lime was
lower than 0·1% by the phenyl formic acid titration method 4%
(GB/T 176 (AQSIQ, 2008)), indicating that the clinkering
process is complete at 1270°C. Figure 2 also shows the 3%
effect of the addition of borax on the stabilisation of high-
3
temperature belite polymorphs (α′-forms). It is seen that the 2% 3
intensity of α′-C2S increases gradually as the addition of borax
increases from 2% to 5%. Correspondingly, the increase in the 2
0% 2
formation of α′-C2S means the decrease in the formation of
β-C2S. The peaks of β-C2S are not obvious when the dosage of 10 20 30 40 50 60
borax is higher than 3%. The results indicate that the addition 2θ: degrees
of borax can significantly promote the stabilisation of high- (b)
temperature belite polymorphs in sulfate-rich BSA clinkers.
The doping mechanism of boron (B) in belite is reported and Figure 2. XRD patterns of sulfate-rich BSA clinkers doped with
different quantities of borax: (a) C1; (b) C2
the results support the substitution of silicate groups by tetra-
hedral borate groups with the concomitant substitution of
calcium by boron for charge compensation (Cuesta et al.,
2012). borax. As shown in Table 4, the phase compositions of these
clinkers are quite close to the targeted values. With the increase
Table 4 presents the results of the quantitative XRD analysis of borax addition in the raw materials, the α′-C2S content
of sulfate-rich BSA clinkers doped with different quantities of in active sulfate-rich BSA clinkers increases accordingly.

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 Advances in Cement Research Active sulfate-rich belite
sulfoaluminate cement
Shen, Yang, Zhang and Qian

Table 4. Quantitative phase compositions of sulfate-rich BSA 20

10
clinkers doped with different quantities of borax (wt%)
8
Cement Borax C4A3S α′-C2S β-C2S C4AF CS

Heat flow: mW/g

2%
15 6
C1 0 34·7 0 47·3 9·6 8·4

Heat flow: mW/g

2 35·4 12·0 34·4 10·1 8·1 4
3 33·9 24·2 23·2 10·3 8·4
2
4 36·7 37·8 7·2 9·8 8·5 10 0%
5 35·6 42·3 3·8 9·5 8·8 3% 0
0 0·5 1·0 1·5 2·0
C2 0 41·0 0 30·0 10·5 18·5
Time: h
2 41·7 15·4 14·7 9·9 18·3
3 40·8 22·3 9·0 9·8 18·1 5
4 40·4 26·7 5·0 9·7 18·2
5 41·3 29·0 1·8 9·8 18·1
0
0 5 10 15 20 25 30
Time: h
40
(a)
0% 2%
3% 4% 350
Compressive strength: MPa

35 5% 0%
300 2%
3% 2%
250 3%
30
Heat: J/g

200
0%
150
25
100

20 50
7d 28 d 56 d
(a) 0
0 5 10 15 20 25
50 Time: h
0% 2% (b)
45 3% 4%
Figure 4. Effect of boron trioxide (B2O3) content on isothermal
Compressive strength: MPa

5% conduction calorimetry of cement C2: (a) heat flow; (b) cumulative

40 heat

35
Compressive strength
30 The strength developments of the sulfate-rich BSA cements,
prepared with the addition of borax, are illustrated in Figure 3.
25 As shown, the cement pastes activated by borax achieve higher
strengths compared with the reference cement paste. This may
20 be ascribed to the activation of belite and the increased
7d 28 d 56 d hydraulic properties of belite. After 7 d of hardening, the com-
(b) pressive strengths of the clinkers doped with different quan-
Figure 3. Compressive strength of sulfate-rich BSA cements tities of borax increase gradually and the increase is
doped with different quantities of borax: (a) C1; (b) C2 remarkable, especially at 56 d. This indicates that the hydration
of α′-C2S occurs mainly after 7 d and the faster hydration rate
of α′-C2S than β-C2S contributes to the increase in the com-
pressive strength. The hydration of α′-C2S usually takes place
When the dosage of borax reaches 5%, the content of β-C2S is after 3 d and the compressive strength of the activated cements
lower than 5% and the change in polymorphs is basically com- increases mainly after 7 d (Li et al., 2007). It can also be seen
plete. Additionally, the contents of ye’elimite, ferrite and anhy- that the dosage of borax has a remarkable effect on the com-
drite are constant in all sulfate-rich BSA clinkers. pressive strength of these activated cements. The cement pastes

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 Advances in Cement Research Active sulfate-rich belite
sulfoaluminate cement
Shen, Yang, Zhang and Qian

1 Ettringite 1 Ettringite
2 Ye’elimite 2 Ye’elimite
3 Belite 3 Belite
4 Monosulfate 4 Monosulfate
5 Strätlingite 5 Strätlingite
1 3
1 3
2 1 1 3
1 1 3 2 3 1
1 3 2 1 1 3 3
1 111 56 d 2 3 1
5 1 1 3 56 d

5 4
28 d 4
28 d

2
23 7d 2 7d

10 20 30 40 50 60 10 20 30 40 50 60
2θ : degrees 2θ : degrees
(a) (a)

1 Ettringite 1 Ettringite
2 Ye’elimite 2 Ye’elimite
3 Belite 3 Belite
4 Monosulfate 4 Monosulfate

2 3 2
1 1 1 1
1 1 1 3
1 2 3 1
1 1 31 3
1 1 3 3 2 1 1 2
56 d 1 1 3 56 d
2

4 28 d 4
28 d

7d
7d

10 20 30 40 50 60
10 20 30 40 50 60
2θ : degrees
2θ : degrees
(b)
(b)
Figure 5. XRD patterns of sulfate-rich BSA cements hydrated for
7, 28 and 56 d: (a) C1; (b) C2 Figure 6. XRD patterns of sulfate-rich BSA cements doped with
2% borax hydrated for 7, 28 and 56 d: (a) C1; (b) C2

activated by 2% and 4% borax exhibit much higher compres-

sive strength than those with 3% and 5% of borax. Therefore, (Winnefeld and Barlag, 2009; Winnefeld and Lothenbach,
an appropriate dosage of belite activator should be taken into 2010; Zhang and Glasser, 2002). Compared with the reference
consideration to obtain high mechanical strength. cement, the activated cements have a higher heat flow. The
acceleration period ranges from approximately 2 to 10 h for all
Isothermal calorimetry the three cements. The heat flow during this period is mainly
The heat evolutions of the sulfate-rich BSA cements were associated with the depletion of calcium sulfate and the for-
studied by conduction calorimetry and the results are given in mation of sulfoaluminate hydrates (Bullard et al., 2011; Dovál
Figure 4. The formation of high-temperature belite poly- et al., 2005; Ioannou et al., 2014). The first main hydration
morphs results in different heat flows at a given time. The heat peak appears at 3 h for the inactive cement and at 5 h for the
release during the initial period, ranging from 0 to 0·5 h, is activated cements. Compared to the inactive cement, the acti-
characterised by the dissolution of ye’elimite, the initial pre- vated cements react faster and yield the stronger heat flow,
cipitation of hydrates, as well as the wetting of the system especially for the cement activated by 2% borax, which has the

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 Advances in Cement Research Active sulfate-rich belite
sulfoaluminate cement
Shen, Yang, Zhang and Qian

highest heat flow. A second heat flow maximum occurs at Hydration of activated sulfate-rich BSA cements
approximately 8 h for the three cements. Also, the addition of The changes of the hydration products were determined by
borax slightly decreases the accumulated hydration heat up to XRD, and the patterns are presented in Figures 5 and 6. As
5 h. After this period of time, the activated cements display shown in Figure 5, anhydrite has been almost fully consumed
much higher values of total heat output, especially for the and there is also part of non-reacted ye’elimite after 7 d of
cement activated by 2% borax. hydration. Ettringite has formed as a new crystalline phase due
to the hydration of ye’elimite, and traces of monosulfate are
detectable after 28 d. Meanwhile, the intensity of ettringite
peaks appears to decrease as a result of the partial decompo-
1 Ettringite sition and the transformation to monosulfate. The belite phase
2 Ye’elimite
is hydraulically inactive at early ages, and its peaks remain
3 Belite
4 Monosulfate constant before 28 d. In addition, strätlingite has formed from
5 Strätlingite the reaction of belite and gibbsite in hydrated cement C1.
1 3 Figure 6 also shows XRD analysis of activated cements at
1 1 3
12 different ages. It can be seen that the crystalline phase assem-
1 3
1 1 3 3 blage of the activated cements is similar to that of non-
1 1 4%
activated cements. Moreover, belite activated with 2% borax
hydrates after 28 d from the decreased intensity of belite peaks.
2% But the hydration of belite is not significant, possibly because
2
of the relatively low-reactivity nature of C2S even with the
5 4 2 0% α′-C2S form. Portlandite from the hydration of α′-C2S is never
detected, possibly because the expected amount of this phase
is quite low.
10 20 30 40 50 60
2θ : degrees The XRD analysis of cement C1 activated with different quan-
Figure 7. XRD patterns of activated cement C1 hydrated for 56 d tities of borax is presented in Figure 7. Ettringite peaks
become stronger as the dosage of borax increases. This

SEM HV: 20·00 kV WD: 14·03 mm VEGA3 TESCAN SEM HV: 20·00 kV WD: 9·959 mm VEGA3 TESCAN
SEM mag: 5·00 kx Det: SE 5 µm SEM mag: 5·00 kx Det: SE 5 µm

SEM mag: 5·00 kx Date(m/d/y): 12/04/2014 SEM mag: 5·00 kx Date(m/d/y): 12/04/2014

(a) (b)

Figure 8. SEM images of cement C1 hydrated for 28 d: (a) 0%; (b) 2%

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 Advances in Cement Research Active sulfate-rich belite
sulfoaluminate cement
Shen, Yang, Zhang and Qian

indicates that the addition of borax not only induces the acti- Bullard JW, Jennings HM, Livingston RA et al. (2011) Mechanisms
vation of belite but also promotes the hydration of ye’elimite. of cement hydration. Cement and Concrete Research 41(12):
1208–1223.
The decrease of strätlingite peak intensity shows that the acti-
Chatterjee AK (1996) High belite cements – present status and future
vation of belite hinders its reaction with gibbsite. technological options: part I. Cement and Concrete Research 26(8):
1213–1225.
The SEM investigations were performed to observe the micro- Cuberos AJM, De la Torre AG, Ălvarez-Pinazo G et al. (2010)
structures of the hydrated cements. The images of the pastes Active iron-rich belite sulfosluminate cements: clinkering
and hydration. Environmental Science and Technology 44(17):
hydrated for 28 d are presented in Figure 8. It is shown that
6855–6862.
the morphology of ettringite is different in the two pastes. Cuesta A, Losilla ER, Aranda MAG, Sanz J and De la Torre AG
Column-shaped ettringite is observed in the inactive paste (2012) Reactive belite stabilization mechanisms by
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The result indicates that the activation of belite can affect the 598–606.
Dovál M, Paloui M and Kovár V (2005) Heat evolution and mechanism
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Conclusions Gartner E (2004) Industrially interesting approaches to ‘low CO2’
The activation of belite in sulfate-rich BSA cements has been cements. Cement and Concrete Research 34(9): 1489–1498.
investigated in this work. Borax was used to act as an activator Ghosh SN, Bhaskara Rao P, Paul AK and Raina K (1979) The chemistry
of dicalcium silicate mineral. Journal of Materials Science 14(7):
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1554–1566.
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calcium sulfoaluminate-calcium sulfate-fly ash cement.
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Acknowledgements Marroccoli M, Pace ML, Telesca A and Valenti GL (2010) Synthesis of
The authors gratefully acknowledge the financial support calcium sulfoaluminate cements from Al2O3-rich by-products from
from National Nature Science Foundation of China (NSFC) aluminium manufacture. Proceedings of the 2nd International
under grant no. U1202275 and Jiangsu Planned Projects for Congress on Sustainable Construction Materials and Technologies,
Ancona, Italy, pp. 615–624.
Postdoctoral Research Funds (1601016B).
Pace ML, Telesca A, Marroccoli M et al. (2011) Use of industrial
byproducts as alumina sources for the synthesis of calcium
sulfoaluminate cements. Environmental Science and Technology
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