Compositional and Structural Evolution of Calcium Silicate Phases

， ，
HOU Guihua1, GAO Xiaojiao1 2, LU Bao1 3, ZHU Huajun1, CUI Entian1 and ZHANG
Qinfang1*
1. Key Laboratory for Advanced Technology in Environmental Protection of Jiangsu Province,
Yancheng Institute of Technology, 224051, China
2. Department of Materials Science & Engineering, Changzhou University, Changzhou, Jiangsu,
213164, China.
3. Department of mechanics and material engineering, Hohai University, 210098, China

Abstract: Calcium silicate is the main mineral of Portland cement clinker, in which low heat
consumption and exhaust emissions require low calcium content. Therefore, exploring the presence of
low calcium minerals will lay the foundation for the design and research of Portland cement clinker
with energy-saving and low-emission. Using an efficient structure search method based on a particle
swarm optimization algorithm and experimental technique, we study the compositional and structural
evolution of calcium silicate phase, i.e., probable existing mineral phase from combining calcium oxide
with silica oxide, preparing condition and hydration properties of 3CaO·2SiO2 (C3S2). Our results
show that five calcium silicate phases including C3S, C2S, C3S2, CS and CS2 are stable. C3S2, less
concerned phase, forms under the temperature arranged from 1100℃to 1460℃and its hydraulic
activity is low in the room temperature with the hydration productions containing C-S-H gel and
Ca(OH)2. Under the condition of 3-day hydrothermal curing at 80℃, its compressive strength reaches
8.6MPa for 2×2×2 test block.

Originality
Variable stoichiometry structure prediction method has been used to study the structural evolution of
calcium silicate phase. The variable composition compounds containing calcium and silica oxides are
found to be only stable with the ratio of 3:1, 2:1, 3:2, 1:1 and 1:2.
To the best of our knowledge, there are still few studies on the crystal structure information of C3S2, not
to mention the investigation of its hydration properties. In this paper, the solid state sintering process is
adopted for the preparation of C3S2 with the starting materials of CaCO3 and SiO2 analytical reagent.
Its diffraction pattern is measured by XRD and compared with computational methods. Under the room
temperature and hydrothermal curing condition at 80℃, its mechanical properties and its morphology
are analyzed.

Keywords：Calcium silicate, structural evolution, C3S2, saving energy cement

1
Corresponding author: qfangzhang@gmail.com, Tel: +86-515-88298920, Fax:
+86-515-88298920

1
1. Introduction
Since the Portland cement invention, the research hotspot in this field was to reduce the
heat consumption of clinker and exhaust emission during calcinations process. The CaO
content in Portland cement was about 65%, and about 511kg CO2 was produced per 1 ton
clinker. Therefore, the emitted CO2 during burning Portland cement clinker was originated
form the decomposition of limestone (CaCO3). Moreover, the heat consumption of CaO
accounted for about 60 percent of the total heat consumption. As a result, low CaO content
not only can reduce the thermal consumption of clinker and the emission of CO2 and exhaust
gas, but transform the limestone mine with lower CaO content and the industrial waste of
higher CaO content into valuable raw materials. As a consequence, the study on reducing the
calcium content of Portland cement clinker is of terribly important. On the basis of such a
consideration, many studies on Belite have been made. Unfortunately, the hydrating activity
required rapid cooling velocity, which hindered its industrialization. By contrast, it was
important to investigate whether there were other low-calcium minerals except the familiar
C3S, C2S, and CS, formed between CaO and SiO2. In this study, using an efficient structure
search method based on a particle swarm optimization algorithm and experimental technique,
we studied the compositional and structural evolution of calcium silicate phase, and further
investigated the preparation condition and hydration property of 3CaO·2SiO2 (C3S2).
2. Experimental
2. 1. Experimental section
A computing simulations of reaction between CaO and SiO2 was conducted by calypso
program. The C3S2 and cement clinker were synthesized using CaCO3，SiO2，Al2O3, and Fe2O3
as raw materials. All chemicals, were of analytic reagent grade and used without further
purification.
2. 2. Characterization
X-ray diffraction (XRD) patterns of samples were recorded on a D max/RB X diffractometer.
Transmission electron microscopy (TEM) images were taken with a FEI QUANTA2000
transmission electron microscope.
3. Results and Discussion
3.1. Crystal structure predictions to the mineral from reaction CaO with SiO2
The crystal structure predictions were performed with particle swarm optimization (PSO)
method as implemented in the CALYPSO code. The PSO algorithm offered an efficient and
fast way to obtain reliable structures with only the input of chemical composition. It searched
for structures with space group symmetry in combination with density functional theory
calculations. We investigated the phase stabilities and structural changes of various CaO-SiO2
(C-S) systems without external pressures. The relative formation enthalpy of C-S systems was
calculated by using fractional representation (CaO)x(SiO2)y with respect to the CaO and SiO2
as ΔH=( H(CaO)x(SiO2)y- xHCaO - yHSiO2 )/(x+y) (1)
The enthalpy H for each compound was obtained for the most stable structure searched by the
CALYPSO method. The convex hulls depicted in figure 1 shows the metastable phases, which
have negative relative enthalpy of formation.

2
 CaO CaO. 2SiO2 3CaO. 2SiO2 3CaO. SiO2 SiO2
CaO. SiO2 2CaO. SiO2

0.1

DH(eV/atom)
-0.1

-0.2

-0.3

-0.4

-0.5
0.0 0.2 0.4 0.6 0.8 1.0

Figure 1 Relative enthalpies of formation per atom for different C-S Phases.
We identified the formation of five stoichiometric calcium silicate phase (CS2, CS, C3S2, C2S,
and C3S, shown in figure 2) having unforeseen structural features that might be
experimentally synthesizable over a wide range of temperature and pressures.

Figure 2 Predicted structures of C-S at ambient pressures. (a) CS2. (b) CS. (c) C3S2. (d) C2S (e) C3S.
It was much interested to us that the C3S2 phase was not so well studied systematically which
had lowest relative enthalpies of formation under ambient pressures and quite similar crystal
field with C2S (The average interatomic distances between Ca(Si) and O were much close).
3.2. Pure C3S2 forming process
C3S2 was synthesized by solid state synthesis method using CaCO3 and SiO2 as raw materials,
as shown in figure 3. When the reaction temperature was 1200℃, peaks ascribed to C2S
appeared, and there were still unreacted CaO and SiO2. But no C3S2 peaks were detected. As
temperature rising to 1320℃, the diffraction peaks ascribed to C3S2 were detected, and the
peak strength of C2S、CaO and SiO2 declined. It was obviously that C3S2 was prepared by
reacting C2S, CaO and SiO2. Rising to 1460℃, all peaks except for these of C3S2 disappeared.
At 1480℃, peaks ascribed to C2S and SiO2 were detected again, indicating that C3S2
decomposed into C2S and SiO2. Thus it could be concluded that the formation temperature
and decomposition temperature of C3S2 were 1300℃ and 1480℃, respectively.

3
 C3S2 CaO
C2 S SiO2
 
  
    1480C
   
   
    1460C


 
     1420C
         

 

   1320C
 
        
 


   
    1200C
  
  

10 20 30 40 50 60 70
2()

Figure 3 The formation process of pure C3S2

To date, only a few papers on C3S2 have been published. Shinsuke named it rankinite
[Shinsuke S. et al., 1976.]. C3S2 also exsited in mines and slag and the corresponding
formation temperature and decomposition temperature were 1100℃ and 1460℃, respectively
[Hillret M., et al., 1991; Engel V. S., et al., 2013.]. The formation temperature was different
from that of ours, which originated from the different chemical reactivity of raw materials and
the intermediates. As mentioned, in our study, the formation temperature of C3S2 was higher
than that of C2S. So the chemical reactivity of C2S had significant influence on the formation
temperature of C3S2.
3.3. Burnability of clinker with different C3S2 content
To investigate the influence of liquid phase on C3S2 formation and the performance of
Portland cement clinker, we synthsized clinker samples with different cement clinker
compositions and discussed their fromation processes. Figure 4 gave the corresponding XRD
patterns.

4
 C3A C3S2
C4AF C2S


SiO2 3-75%C3S2

 12%C3A
     13%C4AF
 


 2-70%C3S2
13%C3A
  
  
  17%C4AF
   


 1-65%C3S2

  16%C3A
  


19%C4AF
 

10 20 30 40 50 60 70 80
2()

Figure 4 XRD patterns of clinker samples with different cement clinker compositions (reaction
temperature: 1400℃; calculation time: 1h)
In figure 4, the mineral composition of sample 1, 2, and 3 were (C3A 16%, C4AF 19%, C3S2
65%), (C3A 13%, C4AF 17%, C3S2 70%), and (C3A 12%, C4AF 13%, C3S2 75%), respectively.
Among them, C3A and C4AF were collectively referred to as fluxed minerals. The fluxed
minerals in sample 1 accounted for as high as 35 percent. Only the peaks ascribed to C3A,
C4AF, and C3S2 were detected in clinker product, and all the peaks were clear and symmetric,
which indicated that the composition of sample 1 conformed with what we designed. The
fluxed minerals in sample 2 accounted for about 30 percent. The XRD pattern of sample 2
was similar with that of sample 1, but the peaks had poor symmetry. For sample 3, the fluxed
minerals accounted for about 25 percent. As shown in figure 4, compared with these of
sample 1 and 2, there were new peaks appered in samples 3, which can be scribed to C2S and
SiO2, and the symmetry of all peaks was poor. From what has been discussed above, it would
be reasonable to believe that during synthesis process, the liquid phase of clinker had great
influence on the formation of C3S2 and the formation of C2S was easier than that of C3S2
under the similar conditions.
3.4. C3S2 hydrating performance
Figre 5 presented SEM figures of hydrated C3S2 samples under different curing conditions. As
can be observed from figure 5a，at 25℃, pure C3S2 was loose after 28d hydration. The
hydration products were few and only distributed on the surface of particles. The hydration
activity of C3S2 under this curing condition was low. But when the curing temperature was
90℃, pure C3S2 became one flesh (figure 5b), exhibiting high hydrating activity. The
hydration products should be C-S-H.

5
 a: at 25℃for 28d b: at 90℃for 28d
Figure 5. SEM figures of hydrated C3S2 samples under different curing conditions
3.5. C3S2 compressive strength
Table 1 showed the compressive strength of C3S2 (2×2×2 test block) under different cooling
conditions and curing conditions. As seen in Table 1, the cooling conditon had no discernible
effect on the hydrating perfprmance of C3S2. But hydrothermal curing affected greatly on the
compressive strength of C3S2. Compared with sample 1, the compressive strength of sample 3
after 3, 7, and 28d maturation had driven a 3, 5, and 3-fold increase, respectively. The highest
compressive strength was 8.6 MPa. But overalll, the hydrating activity of C3S2 was low.
Tab 1. the Compressive strength of C3S2
Compressive strength/MPa
sample cooling condition curing condition
3d 7d 28d
1.pure C3S2 rapid cooling 25℃ 2.2 3.5 12.1
2. pure C3S2 slow cooling 25℃ 2.1 3.3 11.9
3. pure C3S2 rapid cooling 80℃ 8.6 19.8 33.2
4. pure C3S2 slow cooling 80℃ 8.3 19.1 28.2
4. Conclusions
Our results showed that five calcium silicate phases including C3S, C2S, C3S2, CS, and CS2
were stable by the compositional and structural evolution of calcium silicate phase, i.e.,
probable existing mineral phase from combining calcium oxide with silica oxide. C3S2 formed
under the temperature arranged from 1300℃to 1460℃. Beyond 1460℃, C3S2 decomposed
into C2S and SiO2. Under the condition of 3-day hydrothermal curing at 80℃, its compressive
strength reaches 8.6MPa for 2×2×2 test block.
Acknowledgements: Financial support of the work by the Natural Science Foundation of
Jiangsu Province (No. BK2012676, BK20130428, BK20140463) and National Key
Technology R&D Program (2013BAC13B01-03) is greatly acknowledged.
References
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Journal, 8, 240-246.
-Hillret M., Bo S., Wang X., 1991. A reevalution of the bankinite phase in the CaO-SiO2 system,
Calhlad, 15, 53-58.
-Engel V S., Muratalie V Z., 2013. The exothermal effect upon Interaction of calcium and silicon
oxides, Thernophysical Properties of Materials, 51, 645–651.