Journal of Building Engineering 68 (2023) 106001

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Journal of Building Engineering

journal homepage: www.elsevier.com/locate/jobe

Effect of using grounded coral sand on hydration and strength

development of portland cement paste: Experimental and GEMS
modelling investigation
Haiyan Ma, Haotian Fan *, Hongfa Yu **, Xinwen Peng
Department of Civil and Airport Engineering, Civil Aviation College, Nanjing University of Aeronautics and Astronautics, Nanjing, 210016, China

A R T I C L E I N F O A B S T R A C T

Keywords: The use of coral sand is mainly focusing on how to use it as aggregate in marine areas, much fewer
Coral sand powder studies have been conducted to investigate its usage as SCM (supplementary cementitious ma­
Strength development terial) after being grounded into powder. In this context, the influence of CSP(coral sand powder),
GEMS modelling used as SCM, on the hydration and strength development of Portland cement paste was investi­
Hydraulic products gated. In order to describe the hydration process, Experiments including Isothermal calorimetry,
Hydration
XRD and TG analysis were used, along with the GEMS modelling system. The effect of CSP
content, curing temperature and w/c were investigated in this study. The result shows that coral
powder plays a nucleus effect in the process of cement hydration, which promotes the early age
hydration of cement. Low coral powder substitution rate of no more than 10% can enhance the
strength development of CSP concrete. However, with the increase of age and replacement rate,
the coral powder shows a dilution effect which would slower the exothermic rate of the cement
system. As to the hydraulic products. The results shows that the form of aluminum-containing
hydration products in the coral powder-cement-based system is closely related to the content
of coral powder. Apart from these, the increase of the w/c ratio is conducive to increase the
hydration rate and hydration product content of coral powder-Portland cement systems. And with
the increase of hydration temperature, the hydration rate of the cement system and the genera­
tion rate of hydration products are accelerated, although the main type of hydration product is
not changed.

1. Introduction
The construction of infrastructure on open sea island consumes huge amount of concrete, which is made from material including
cement, aggregate and fresh water. These kinds of material usually need long distance shipping since they are not locally available in
the open sea. With the purpose of reducing the cost, the coral sand, a kind of material which is widely spread in pacific and Indian
Ocean, has been widely used as a construction material in many region.
The coral sand was firstly used as concrete aggregate on pacific islands during the second world war by US marines. A lot of military
facilities were established using coral aggregate concrete (CAC). After the war, during the 1950s, The civil engineering laboratory of

* Corresponding author.
** Corresponding author.
E-mail addresses: mahaiyan@nuaa.edu.cn (H. Ma), 3287916304@qq.com, fanhaotian@nuaa.edu.cn (H. Fan), yuhongfa@nuaa.edu.cn (H. Yu), 1094420735@qq.
com (X. Peng).

https://doi.org/10.1016/j.jobe.2023.106001
Received 21 December 2022; Received in revised form 17 January 2023; Accepted 29 January 2023
Available online 3 February 2023
2352-7102/© 2023 Published by Elsevier Ltd.
H. Ma et al. Journal of Building Engineering 68 (2023) 106001

US navy firstly published the investigating reports about the performance of CAC, and established the standards about how to use it.
The investigations in the following 6 decades were mostly focusing on the how to improve the performance of using coral sand as
aggregate. In 1964, Narver D L [1], in 1974, discovered that CAC has early strength characteristics and slow intensity growth in the
later stages. The results showed that the strength of CAC can increase by up to 17% after 28 d of hydration, while at 91d, the strength is
lower than that of concrete using Portland cement. In 2013, Professor Yu Hongfa from Nanjing University of Aeronautics and As­
tronautics [2] first proposed the theory of slurry-rich concrete, using cement mortar to wrap coral aggregate, designing C55
high-strength CAC, and studying the effect of water-to-adhesive ratio and curing time on CAC compressive strength. The results
showed that in the early stage of curing, the growth rate of CAC compressive strength was relatively fast, and the growth rate of
compressive strength slows down and stabilizes after the age of 7 days. In 2017, Dabo [3] studied the influence of the preparation
method of high-strength CAC on the cube compressive strength, developed the full curve law on uniaxial compressive stress-strain, the
corrosion performance of steel reinforcement, the mechanical properties of reinforced concrete beam and column components and
crack development and other failure forms.
Apart from being used as aggregate, after being finely grounded, the coral sand which has very high chemical content of CaCO3,
similar to the crushed limestone, can be used as supplementary cementitious material (SCM). The effect of Lime stone powder on the
mechanism of action as cement composite has been widely investigated.
In 1938, Bessy [4] was the first researcher observed the existence of calcium carboaluminate hydrate in the paste containing
limestone powder. Ten years later, Deniels A [5] proposed that due to its small size, the limestone powder played a role as filler,
improving the porosity and compressive strength of concrete. In 1976, Soroka I et al. [6] investigated the nucleation effect of limestone
powder. And discovered that in the process of cement hydration, limestone powder can adsorb Ca2+, providing a location for the
precipitation and growth of hydrated C–S–H, and accelerate the hydration reaction of cement.
On the base of these, in these few years, the use of CSP as supplementary cementitious material was more and more frequently
studied, Sato T [7] investigated the strength and durability of the concrete using coral powder as cementitious materials, The results
indicated that the incorporation of coral powder could reduce the strength and durability of cement mortar. But at the same time
promote the generation of single-carbon hydrated calcium carbonate in cement systems, hence enhancing the interface structure of
cement slurry. Hu Shia et al. also. [8] studied the effects of coral sand powder (CSP) on the hydration and mechanical properties of
Portland cement slurry within 1–90 days of conservation age and found out that the addition of coral powder can fill the porous
structure of concrete under long-term curation. And the use of coral powder with the replacement rate of 5% cement can improve the
1~7d compressive strength of the mortar.
During the hydration of CSP-PC paste, the main components of cement clinker including C3S, C2S, C3A, and C4AF react at different
rates to produce CH, CC(calcite), AFT (ettrigite), HC(portlandite), MC (half and Single carbon hydrates of aluminium calcium car­
bonate)portlandite, ettringite, monosulfoaluminate, hydrogarnet and other trace hydration products. In 2020, Hu Shia et al. [9]
studied the hydration dynamics, microstructure development and mechanical properties of the coral powder-calcium sulfate cement
binary paste within the curing age of 90 days. The properties of aluminate cement mixed with different contents of coral powder (5%,
15% and 25%) were studied through different experimental tests. The results showed that coral powder reacted with calcium sulfate
and turned into semicarb hydrated calcium carbonate aluminate. In 2021, Wang Zhuolei et al. [10] used CSP to replace Portland
cement with the rate of 10%, 20%, 30%, and got the result that addition of CSP does not change the main hydration product species of
Portland cement while it can extend the condensation time and reduce the hydration exothermic excalorific rate of cement-based
materials; cement partially replaced with CSP has lower resistivity and wave absorption of cementitious materials; In the same
year, Yue Qin [11] investigated the effect of CSP content on the cement paste using sea water, the result showed that the CaCO3 in coral
powder helps promote the hydration of cement. Apart from this, the MgCl2 salt in sea water has the dual effect of reducing the stiffness
of the cement mortar specimen and strengthening the aggregation of coral powder particles. The coupling of coral powder and MgCl2
salt affects the microstructure and macroscopic mechanical properties of the mortar, and the role of the two is mutually restrictive.
To investigate the mechanical properties and hydraulic procedure of cement paste containing CSP, apart from basic experimental
test, a numerical simulation should also be simultaneously conducted to help us get the information which can hardly be precisely
tested through experiments.
The simulation of the cement hydration procedure should be conducted on the base of reliable hydrothermal database. Since K. K.
Kelly and E. G. King published the first hydrothermal database in 1932, the system has been continuously complemented and refined
by a lot of researchers including Welch J. H. [12](1959), Berman R.G. [13](1987), and D. Damidot [14](1995). Three sets of latest data
bases containing complete information of cement hydration were selected to be used in this research: Firstly the Cemdata18 developed
by Barbara Lothenbach et al. (2018) which Secondly the PSI-Nagra database developed by Swedish institution in 1992 [15], and
thirdly SUPCRT92 database.
Different kinds of software including GEMS [16], Thermo-Cale [17], FactSage [18]and GWB [19] have been developed through the
paste few decades to conduct the thermodynamic simulation.
The model of GEMS takes the chemical composition, water content, curing temperature, environment pressure, the content of
clinker as the input data, and put out the information of the evolution of the quality of hydration products of cement cementitious
system with time, the evolution of the volume of hydration products of cement cementitious system with time, and the evolution of the
ion concentration of pore solution of cement cementitious system with time.
GEMS system has great advantage in huge data base which includes PSI-Nagra, SUPCRT92 and third-party database,
Thermo-Cale has advantage in flexibility, however, this model is lacking in thermodynamic data, the supporting engine is not
advanced enough for the hydration analysis.
Software of FactSage can calculate the data of molten salts, oxides and slags precisely, which however, can hardly model the data of

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H. Ma et al. Journal of Building Engineering 68 (2023) 106001

cement paste.
GWB has the advantage of very little limit on the reaction environment, but meanwhile has the disadvantage of extreme high
requirement on the accuracy of imputed data.
With considerate comparison of the strengths and weaknesses of every software, GEMS was finally selected due to its suitability for
the hydration of cement.
The objective of this study was to reveal the effect of CSP (coral sand powder) with different dosage on the PC cement paste through
studying the hydration behavior and strength development of coral powder-cement composite cementitious materials,. The methods
including isothermal calorimetry, XRD ray method and TG thermogravimetric analysis test were used to analyze the hydration process
and hydration product composition of coral powder-cement slurry, and the thermodynamic simulation software (GEMS) is used to
simulate the influence of different content coral powder on the hydration product and hydration process of Portland cement
cementitious material. The results and conclusions of this study can hopefully provide a reference for more rational use of coral reef
resources in construction of island and reef projects.

2. Experiment program
In this section, different mix proportions for CSP-PC pastes were designed to investigate the influence of different replacement rate
on the strength development and hydration procedure of it.

2.1. Material
The PC used in this experiment is PI42.5 produced by Nanjing Hailuo Co., containing 63.04% of CaO 21.12% of SiO2 5.32% of
Al2O3, in the chemical aspect 55.883% of C3S, 18.54% of C2S,8.59% of C3A in the mineralogical aspect, (the detailed information is
shown in the following Table 1 and Table 2).
The coral powder used in this experiment is produced by grounding natural dried coral sand from south China Sea. Fig. 1. The
average surface area of the powder is 645 m2/kg, with detailed particle size distribution shown in the following Fig. 2. According to the
result of XRD test (Fig. 3), The main chemical content of the coral sand is shown in Table 3.

2.2. Mix proportion and specimen preparation

To investigate the effect of coral powder with different replacement rate on the PC, The mix design of paste specimens is shown in
the following Table 4, with the w/c ratio of 0.5.

2.2.1. Samples of two different shapes are prepared

The first kind of samples are cubes of 20mm × 20mm × 20 mm, as shown in Fig. 4 which are used to conduct the compressive
strength test, XRD test and TGA (thermogravimetric experiment). The samples are prepared according to Chinese standard GB/T1346-
2001, which were cured under standard condition (20 ± 2 ◦ C) humidity of 95% for 3d, 7d and 28d. Some of the samples are grounded
into powder to conduct the XRD and TGA tests.
The second type of samples are prisms with the size of 20mm × 20mm × 80 mm as shown in Fig. 5, to conduct the flexture strength
test.

2.3. Test methods

2.3.1. Strength tests
Cube compressive strength and three-point flexural strength tests are conducted with the help of HG-YH100D press machine at 3,7
and 28days, formulas used to calculate the compressive and flexural strength are shown as follow:
F
fcu =
A

fcu ——compressive strength of paste cube (MPa);

F——Breaking load (kN)
A——Area of surface under pressure (mm2)
Fl
ff =
bh2

ff ——flexural strength of paste cube (MPa);

F——Breaking load (N);
l——Distance between bearing points (mm);

Table 1
Chemical composition of PC (by mass,%).

SiO2 Al2O3 Fe2O3 CaO MgO SO3 Na2O K2O

21.12 5.32 3.35 63.04 1.95 2.69 0.39 0.87

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Table 2
Mineralogical composition of PC (by mass,%).

C3S C2S C3A C4AF MgO Gypsum K2O N2O

55.83 18.54 8.59 10.66 1.95 3.17 0.87 0.39

Fig. 1. Coral sand before and after being grounded.

Fig. 2. Detailed particle size distribution of CSP.

b——Width of specimen (mm);

2.3.2. XRD test

Analysis of XRD was conducted with D/max-2500PC X-ray Powder diffractometer produced by PANalytical B.V company, samples
were separately crushed after 3d, 7d and 28d curing. Powder withdrawn from the central part of samples were added with isopropanol
to stop the hydration process, and then taking XRD test. The Cu target were adopted in X-ray tube, the working voltage and current is
40 kV, and 30 mA, with the step of 0.02o and scanning speed of 8◦ /min, the scanning range (2θ) is 5–70◦ , and the scanning increment is
0.0095o.

2.3.3. TG-DTG test

The analysis was conducted with SAT449 F3 thermal analyzer produced by German Netzsch, samples were prepared with the same
procedure as those used in XRD analysis, the heating rate of TG-DTG test is 10 ◦ C/min with the range of 30–1050 ◦ C.

2.3.4. Isothermal calorimetry test

Isothermal titration calorimetry (ITC) was used to evaluate the exothermic speed and the total energy, with the purpose of assessing

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Fig. 3. XRD test results of CSP.

Table 3
Chemical composition of CSP (by mass,%).

SiO2 Al2O3 Fe2O3 CaO MgO SO3 K2 O Na2O

0.23 0.11 0.13 52.56 1.00 0.46 0.01 0.29

Table 4
Mix design of paste.

Code of samples Coral powder content,% Cement content,kg/m3 Coral powder content,kg/m3 Water content,kg/m3

PC 0 1240 0 620
CSP-10 10 1116 124
CSP-20 20 992 248
CSP-30 30 868 372
CSP-40 40 744 496

Fig. 4. Samples of paste in the shape of cube.

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Fig. 5. Samples of paste in the shape of prism.

the effect of coral powder on cement paste. Eight-channel isothermal microcalorimeter (TAM Air, TA Instruments) was used to record
the exothermic process. Fixed amount, 4g, of cementitious material (PC and coral powder) was mixed with 2.0g of water in ampoule
bottle in the ITC testing facility to assess the hydration heat. 144 h of slurry flow heat was evaluated under the fixed facility tem­
perature of 20 ◦ C.

3. Test results and discussion

The test results which illustrate the effect of CSP on hydration of concrete including compressive strength, XRD result, TG-DTG
analysis and hydration heat are presented in this section. Then the influence of various factors, i.e., the A/C, the W/C and the
aggregate size, on the void content and the compressive strength are investigated in detail.

3.1. Effect of coral powder on the strength development of cement paste

Fig. 6 was developed to show the effect of substituting coral powder for 10%, 20%, 30% and 40% of PC on the strength of cement
paste. And Table 5 was developed to illustrate the exact changes of compressive and flexural strength of CSP paste relative to PC paste.
As can be seen from Fig. 6, the compressive and flextural strength of PC + CSP cementitious mixes generally decreases along with
the increase of CSP content except the one with 10% of CSP. Compared with PC paste, mix with 10% of coral powder developed 3–5%
of higher strength at 3 and 7 days, but 8–16% of lower strength at 28days, While mixes with 20%,30% and 40% of CSP developed lower
strength at all three ages, by up to 52% for mix with 40% of CSP at 28days. The table also showed that the decreasing rate of relative
strength increases not only along with the increase of CSP content, but also along with the increase of curing age. For mixes with
cement partially replaced by 10%–40% of CSP, the relative compressive strength decreases by 13%–22% from 3 to 28days. This
phenomenon indicated that low rate replacement of CSP could enhance the paste strength development at early age. While the increase

Fig. 6. Compressive and flexural strength development of CSP paste.

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Table 5
Relative compressive&flexural strength of CSP paste.

Relative Compressive Strength,% Relative Flexural Strength,%

CSP-10% CSP-20 CSP-30 CSP-40 CSP-10 CSP-20 CSP-30 CSP-40

3 Days 105 99 90 70 104 99 91 78

7 Days 103 94 81 58 104 96 81 70
28 Days 92 81 70 48 84 82 75 58

of replacement rate of PC with CSP could generally result in the decrease of compressive and flexural strength.
The decrease in strength caused by the CSP is understandable since the use of CSP which has lower content of clinker can result in
the lower reactivity of paste. However, as for the mix with low replacement rate (10%) at early age (3,7 days) It is believed that the
reaction between small amount of coral powder and C3A at early stage of hydration produced calcium hydrated carboaloate crystals,
which made up for the strength decrease caused by the lower reactivity at early stage. Apart from this, The Hc and Mc produced
through the reaction between small amount of CSP and PC partially fulfill the pore in the paste, enhanced the strength of paste.

3.2. Result of XRD experiment

Fig. 7 illustrates the XRD analysis of cement paste containing 10,20,30 and 40% of CSP at 3,7 and 28day respectively. Fig. 7 showed
that the main products of the hydration products include: C2S, C3S, CH, CC(calcite), AFT (ettrigite), HC(portlandite), MC (half and
Single carbon hydrates of aluminium calcium carbonate),
It can be observed that Hc, Mc and tricarbonized calcium carboaloate only exists in specimen containing CSP. At the age of 3 days,
Mc can be found in the mixes with 10% plus CSP while Hc and tricarbonized calcium carboaloate can be found in the mixes with 20%
plus CSP. For the mixes at the age of 7 and 28 days, these three kinds of products exists in all mixes containing CSP. This phenomenon
indicates that the existence of Hc, Mc and tricarbonized calcium carboaloate increases gets earlier along with the increase of CSP.
According to the literature [20,21], when being mixed with the rate of 1:3, C3S would react with CaCO3, temporarily change into
tricarbonized calcium carboaloate and finally turned into Hc. As shown in the following formula:

C3 A + 3CC + 11H → C4 ACH11 (Mc)

C3 A + 0.5CC + 0.5CH + 11.5H → C4 AC0.5 H11 (Hc)

3C3 A + 3CC + 32H → C6 AC3 H32

C4 AC0.5 H11 (Hc) + 0.5CC → C4 ACH11 (Mc) + 0.5CH + 0.5H

Apart from this, The strength of peaks in Fig. 7 showed that CaCO3 content continuously increases with the increase of CSP content
especially at the angle of 26◦ , which is understandable since CSP has much higher content of CaCO3.
The result showed that the content of all four different mineral products decrease along with the increase of CSP content and the
development of age, which means that the mineral products content of CSP is much lower compared with PC clinker.
Further analysis was conducted with the software and test method of Topas (Total Pattern Solution), the mineral products content
after different age of hydration is shown in Table 6.
The result indicated that low coral powder substitution rate of no more than 10% can enhance the strength development of CSP
concrete. However, with the increase of age, the coral powder shows a dilution effect which would slower the exothermic rate and
hydration rate of cement paste.

3.3. TG analysis
The TG-DTG results of all concrete samples with different content of CSP are shown in Fig. 8. Generally An increase in the mass loss
and endothermic peak was observed with the increase of CSP content. The first endothermic peak of samples responsible for the
dehydration of AFt and C–S–H was observed at around 100 ◦ C. The second strong endothermic peak corresponding to the decom­
position of Ca(OH)2 was observed at around 420–450 ◦ C. Additionally, the largest peak between 700 and 800 ◦ C, related to the
decarbonation of CaCO3 was observed in samples. The mass loss associated with each of the hydrate products shown in the DTG curves.
The mass loss of mixes at around 100 ◦ C and 420–450 ◦ C corresponding to the decomposition of AFt, C–S–H and Ca(OH)2 decreases
with the increase of CSP content, while opposite trend can be seen between 700 and 800OC. The mass loss caused by the decarbonation
of CaCO3 increases with the increase of CSP content, which is understandable since the increase of CSP which has higher content of
CaCO3 compared with PC has significantly higher content of CaCO3 through hydration procedure.
According to the study of Chen.Y. [22] the mass loss along with the endothermic peak shown in DTG curves between 400 and 500
◦
C is mainly caused by and the only stage of the dehydration of Ca(OH)2. Therefore, the Ca(OH)2 content of different mixes at different
ages were calculated and shown in Table 7.

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Fig. 7. XRD result of paste with different mix design at 3,7 and 28days.

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Table 6
The content of different mineral products at different ages.

Content,% Age PC CSP-10 CSP-20 CSP-30 CSP-40

C3A 3d 2.8 2.4 2.3 2.1 2

7d 1.7 1.4 1.6 0.9 0.9
28d 0.6 0.5 0.5 0.5 0.3

C4AF 3d 6 4.8 4.3 4.1 4.1

7d 3.6 3.3 2.7 2.7 2.4
28d 2.1 2.6 2.5 2 1.2

C2S 3d 8.4 8 7.5 7.5 5.2

7d 6.8 6.4 6.3 6.3 5.1
28d 4.8 4.8 4.1 4 3.2

C3S 3d 21.2 19.8 18.3 16.1 13.1

7d 14.4 13.3 12.8 11 11.2
28d 7.8 6.6 6.5 6.3 5.6

Except the ones with 10% CSP at 3d, Ca(OH)2 content of the pastes generally increases along with the decrease in the amount of CSP
and the increase of age, indicated that the hydration products of specimens generally increases with the increase of time and decreases
of CSP content. As for mixes with 10% CSP at 3d, It is believed that the use of CSP which has lower content of clinker caused the lower
C3S and C2S content of the paste. However, as for the mix with small amount of CSP at early age, Coral powder provides a crystal
nucleation point for the growth of hydration products in the early stage of hydration, accelerates the early hydration of cement paste.

3.4. Effect of coral powder on the hydration heat of cement paste

The method of isothermal calorimetry is mostly used to evaluate the hydration reaction of cement slurry, In this study, which was
conducted by testing the hydration exothermic rate and total amount of exothermic heat. The result showing the effect of different
content of coral powder on the hydration process of cement slurry is illustrated in the following Fig. 9.
The hydration heat release clue is shown in Fig. 9, it is clear that the hydration heat release speed generally decreases along with the
increase of CSP content. The peak value of heat releasing rate of cement paste mixed with 10%,20% 30% and 40% of CSP are 6.17%,
11.87%,18.90% and 28.20% lower compared with Portland cement paste. It is believe that the lower reactivity of CSP compared with
portland cement is the main cause of this phenomenon. For more detailed analysis, the peak area of heat releasing rate got enlarged
and shown in Fig. 10. There are three peaks can be seen. With the increases of coral powder substitution rate, the second exothermic
peak between 21 and 27 h generally faded while the third exothermic peak of the cement cementation system becomes stronger and
stronger between 28 and 34 h. According to the study of Shevalier M [23] and Arora [24], the reaction between CaCO3 and C3A could
produce Mc at the later procedure of hydration, which correspond to the third peak shown in the figure. For the mixes with 20% 30%
and 40% of CSP, the value of the third heat releasing rate peaks are 2.55%, 4.67% and 7.77% higher compared with the corresponding
second peaks. Indicating that higher the content of CSP, stronger the reaction of CaCO3.
Influence of CSP content on the heat of hydration evolutions of mixes are shown in Fig. 10. It is observed that mix with 20% CSP
released the most heat of hydration to the age of 36h, Conversely, at later ages the CSP seems to have an attenuating influence on the
released heat of hydration, pointing to some increase of the dilution effect of clinker. According to the study of Sato. et al. [8], CaCO3,
which takes the main part of CSP, could hinder the hydration of C3A, hence reducing the total amount of hydration heat at later age.
However, It is believed that CSP which is finer compared with PC, helped increased the space for hydration in the cementation system,
enhancing the reactivity of the system at the early age. Therefore, small additions of limestone filler seem to have a negligible influence
on the released heat of hydration.

4. GEMS modelling approach

Software of GEMS has been used in this research to analyze the hydration procedure of cement. Firstly, to confirm the reliability of
the GEMS model, The content of different chemical products in pastes with different replacement rate of CSP along with the increase of
curing age got evaluated and compared with the experimental result of XRD and TG-DTG tests.
Then the further analysis including the effect of replacement rate of CSP, the effect of water cement ratio, and effect of curing
temperature on the hydration of cement system got simulated and shown in the following parts.

4.1. Mathematical models used to evaluate the hydration of cementitious material

Parrot and Killoh’s [25] model along with thermodynamic balance model were selected to calculate the solution in pores and
chemical products through the hydration time in the GEMS system. The hydration ratio of main mineral products including C3S, C2S,
C3A and C4AF got evaluated on the basis of the following three formulas (R1,R2,R3),corresponding to three stages:
Nucleation and growth stages:

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K1
R1 = (1 − αt )( − ln(1 − αt ))1− N1
N1
Formation and hydration shell step:

K2 (1 − αt )2/3
R2 =
1 − (1 − αt )1/3
Diffusion stages:

R3 = K3 (1 − αt )1/N3
In which the αt along with time is:
αt = αt− 1 + Δt • Rt− 1

The effect of surface area of cement and W/C ratio should also be taken into consideration:
( ( ))4
ω
f (ω / c) = 1 + 3.333 • H • − αt
c

ω
αt > H ·
c
In which:
αt ——The hydration rate at the age of t;
αt− 1 ——The hydration rate at the age of t-1;
K1 、 K2 、 K3 ——constant of hydration rate;
N1 、 N3 ——reaction progression;
Δt——interval time;
Rt− 1 ——the smallest value among R1、R2、R3 at the age of t-1;
f(ω /c):effect of water/cement ratio;
H——Critical hydration rate.
Barbara Lothenbach improved this model at 2008 by adding the boundary condition of reaction temperature as shown in following
formula.
Ea
RT = βrh e− R•T

( )4
rh − 0.55
βrh =
0.45
( )
Ea 1 1
− R T − T0
Rt•T = Rt•T0 e

In which:
βrh ——water content;
rh——relative humidity;
Ea ——activation energy;
T——Kelvin temperature;
R——Ideal gas constant;
T0 ——293K。
Solmoi Park concluded the formula above into the following:
( )
∫t { } − ERa T1 − T1
AS 0
Rt•T = min R1 , R2 , R3 f (ω / c)βrh e
0 A0
In which:
AS ——relative surface area of cement;
A0 ——surface area of cement (385 m2/kg)

4.2. The establishment of GEMS model

The procedure of modelling with software of GEMS is shown in the following Fig. 11. Firstly, the mineral products composition of
the PC-CSP mixtures got determined, and then the hydration kinetic model is used to predict the hydration parameters of 4 kinds of

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Fig. 8. TG-DTG results of paste with different content of CSP.

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Table 7
Ca(OH)2 content in cement paste with different content of CSP at different age,%.

PC CSP-10 CSP-20 CSP-30 CSP-40

3d 13.01 13.53 12.98 11.48 10.51

7d 15.76 14.87 14.09 12.38 11.34
28d 20.55 17.85 15.67 14.89 13.22

Fig. 9. The heat release speed of paste with different CSP content.

Fig. 10. Total heat released.

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Fig. 11. Step diagram of GEMS model.

clinker with different coral powder substitution rates at different ages. After that, the hydration parameters are input into GEMS
software, the material parameters and hydration product parameters are converted into program language. The kinetic parameters
modified on the basis of the research of Barbara Lothenbach [26] is shown in following Table 8. Finally, the thermodynamic simulation
data is obtained to simulate the hydration process of the system.

4.3. Selection of data base and chemical elements

The phase assemblage in the samples at 3,7 and 28 days was calculated by GEMS combined with the cement database CEM­
DATA18.1 and the thermodynamic data from PSI-GEMS database, The primary constitutes and the main components of the mixes with
different content of CSP (shown in Table 9) were selected as the input data for the GEMS.

4.4. Validation of GEMS model

The reliability of above-developed GEMS modelling approach and corresponding hydration products material parameters for
ecological concrete were evaluated through the comparison of numerical and experimental results.
Firstly, through the comparison of the numerical and experimental results, types of the chemical products after hydration, the
results of XRD tests and GEMS model show that the main types of hydration products in the simulated coral powder-cement
cementitious material system are highly consistent with the experimental results, as shown in Table 10.
On the base of this, since Ca(OH)2 is one kind of important hydraulic product, the content of which can be precisely evaluated
through TG-DTG test, The Ca(OH)2 content of PC-CSP mixtures at the age of 3,7 and 28days have been calculated and shown in Table 5
in part 3.2. While the corresponding numerical outcomes calculated through GEMS model and the difference between them shown in
the following Table 11 for comparison. The results showed that the difference between numerical results and experimental results are
all below 9%, which indicated that there is high reliability of the GEMS modelling approach is simulating the hydration procedure of
cementitious system. Further analysis about the effect of replacement rate of CSP, w/c ratio, temperature on the hydration of
cementitious system.

5. Result and discussions

Employing the developed GEMS modelling approach and corresponding cement parameters, the hydration properties (content of

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mineral products and hydration products) along with the change of parameters including the content of CSP, curing temperature,
water cement ratio.

5.1. Effect of CSP content

5.1.1. Effect of CSP content on the hydration procedure
With the set of temperature of 20 ◦ C, w/c ratio of 0.5. Changes of main hydration products along with the time developed by GEMS
model is shown in Fig. 12.
The predicted hydrates include C–S–H, CH, AFt and AFm including a small amount of hydrotalcite products as shown in Fig. 12.
When comparing OPC with their CSP containing equivalents, the presence of CSP leads to the increase of calcite content because of the
comparable high calcite content compared with OPC. Meanwhile the increase of CSP content corresponds to the formation of lower
content of C3 (AF)S0.84H (Garnet), OH-hydrotalcite (Hydrotalcite) and C4AcH11(Calcium carbaluminate hydrated). While it is
noteworthy that compared with PC paste of figure (a), mixtures with CSP (b)-(e) witness the disappearance of AFm along with the
existence of C4ACH11. Which indicated that CSP can prevent the transformation of AFm from AFt.
Fig. 12(a) showed that at the first stage, C3A went through the hydration reaction and turned into calcium alumite, followed by the
existence hydrotalgalc (Mg4Al2O7 (H2O)10), which corresponds to the presence of free Mg2+, Al3+, OH− in solution, Along with the
formation of Siliceous garnet ((AlFe|3|O3)[Ca3O3(SiO2)0.84(H2O)4.32])almost at the same time. After that the amount of calcium alum,
calcium silicate hydration and Ca(OH)2 continues to increase. After the running out of the gypsum,.C3A began react with the calcium
alumite, turning into monosulfide hydrated calcium sulfaluminate until the complete hydrate of it. During this stage, the amount of
calcium alum stone continuously decreased while the mass of AFm continues to increase. After which the quantity of AFm remains
basically unchanged.
Compared with Fig. 12 (a) and 12(b)–(e) shows that the conversion of calcium alumite to monothionate is directly limited with the
existence of coral powder. And with sufficient amount of CO2− 3 in solution, C3A forms a monocarbocarbonated calcium carbarate with
CaCO3 instead of forming AFm with calcium alumite, while the rest of the hydration product remains unchanged.

5.1.2. Effect of CSP content on the volume of concrete

The volume change of solid products in cement slurry with the addition of coral powder (0%, 10%, 20%, 30% and 40%) was
simulated by GEMS software, with an initial amount of cementitious material of 100g.
The result shows that the existence of coral powder can not only affect the constituent of hydraulic products but also affect the
volume of pastes. Fig. 13 shows that the volume of paste decreases along with the increase of time. And percentage of paste volume
change decreases along with the increase of CSP content, The volume of the mixes with 10%, 20% 30% and 40% of CSP decreased by
7.11%、6.97%、6.06%、5.28%、4.49% respectively. According to the research of Xiao [27]and Lothenbach [26], specimens con­
taining higher content of calcium would prevent the volume shrinkage of cement paste. Therefore, the high content of calcium is
believed to be the main cause of the decrease in volume shrinkage along with the increase of CSP replacement rate.
According to the result shown in Fig. 14, the reaction between calcium and C3A produced reasonable amount of monosulfide
hydrated calcium sulfaluminate, which could fulfill the pore in the cement paste. Hence the result indicated that addition of CSP could
optimize the pore structure of the paste in the long term.

5.1.3. The effect of CSP content on the chemical content and pH value of pore solution
Fig. 14 was drawn to simulate the change of main elements’ concentration in the pole solution throughout time, the content of CSP
in these specimens increased from Figure (a)–(e).
Elements including Na K Al Si OH and C were increasing along with time, In which Na K increases smoothly because of having no
chemical action through the hydration procedure, while C and Al content slowly increased during the age between 6 h and 30days
along with the amount of CO2− 3 and Al hydroxide melt in the solution. The content of OH increased sharply in the first 2 h of the
−

reaction and then went through a slow increase procedure till the end and concentration of Si increased until the suddenly decrease at
the age of 6 h.
In contrary to elements mentioned above, Ca, Mg and S decreased through out the hydration, The content of S decreased sharply
between 6 h and 2 days because of the running out of gypsum. The concentration of Mg is mainly decided by the content of Brucite,
whose formation caused the continuous decrease of Mg in solution. Apart from these, the decrease of Ca concentration is believed
caused by the decrease of Ca(OH)2 through the hydration.
When comparing Fig. 14 (a) with Fig. 14(b)–(e), it shows that with the addition of CSP, the content of some elements in pore

Table 8
Modified kinetic parameters of cement clinker.

Parameter C3S C2S C3A C4AF

K1 1.5 0.5 1.0 0.37

N2 0.7 1.0 0.85 0.7
K2 0.05 0.02 0.04 0.015
K3 1.1 0.7 1.0 0.4
N3 3.3 5.0 3.2 3.7
H 1.8 1.35 1.6 1.45
Ea (J/mol) 42000 21000 54000 35000

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Table 9
The chemical composition of mixes of PC with different content of CSP.

Replacement rate of CSP,% C3S C2S C3A C4AF Calcite H2O MgO Gypsum K2O N2O

0 55.83 18.54 8.59 10.66 0.00 50.00 1.95 3.17 0.87 0.39
10 50.24 16.69 7.73 9.59 9.66 50.00 1.76 2.85 0.78 0.35
20 44.66 14.83 6.87 8.53 19.32 50.00 1.56 2.53 0.70 0.31
30 39.08 13.98 6.01 7.46 28.99 50.00 1.37 2.22 0.61 0.27
40 33.50 11.10 5.20 6.40 38.65 50.00 1.17 1.90 0.52 0.23

Table 10
Comparison of main types of hydration products between test and simulation.

Result of XRD Modelling result Correspond or not

C–S–H C–S–H ✓
Ca(OH)2 Ca(OH)2 ✓
AFt AFt ✓
AFm AFm ✓
Hc Hc ✓
Mc Mc ✓

Table 11
Test and numerical Ca(OH)2 content of different mix designs at different curing age.

CSP Content 3d 7d 28 d
%
Test value Numerical value Error Test value Numerical value Error Test value Numerical value Error %
% % % % % % % %

0 13.0 13.5 +4.0 15.8 16.5 +4.7 20.5 21.0 +2.1

10 13.5 13.9 +3.2 14.9 15.5 +4.2 17.8 18.9 +6.1
20 12.9 12.6 − 2.6 14.1 14.9 − 6.3 15.7 17.1 +8.9
30 1.5 11.2 − 1.8 12.4 13.4 +8.2 14.9 15.6 +4.8
40 10.5 9.8 − 6.4 11.3 11.7 +3.4 13.2 13.7 +3.8

Error=(Numerical value -Test value)/Test value.

solution changed a lot. Firstly, the Al ion in solution showed sudden decrease with the existence of CSP since Al hydrates would react
with CSP, turning into calcium carboaluminate. Secondly, with the increase of CSP content containing higher percent of CaCO3, the C
element in solution which corresponds to CO2− 2−
3 increased a lot. Thirdly, the content of S element corresponding to the SO4 ion also
decreased with the increase of CSP content, this is mainly caused by loss of single sulfur hydration of sulphoaluminate along with the
formation of calcium carboaluminate. The content of other element kept unchanged through the procedure. Fig. 15 illustrates the
change in pH value of mixes with different CSP content along with time. The alkalinity of pore solution generally increased along with
the hydration age, and specimen with higher content of CSP has slightly lower pH value. Since the pH value of cement pore solution is
widely believed decided by the content of Ca(OH)2, the reaction between CSP and C3S, causing the decrease of Ca(OH)2 content in
mixtures, which corroborates the experimental result shown in Table 5, which is believed to be the main cause of this phenomenon.

5.2. Effect of w/c ratio

In order to analyze the effect of w/c ratio on the hydration process of the PC-CSP system, Content of four different chemical
products including C–S–H, ettigate, Ca(OH)2 and MC with different w/c of 0.3, 0.4 and 0.5 in PC-CSP specimens with 0%
10%,20%,30%,40% of CSP at the age of 3,7,28 and 365 days, were simulated with GEMS. Results were shown in the following Fig. 16.
The content of C–S–H, Ca(OH)2 and MC increased with the increase of w/c ratio and curing age while ettigate content went through
opposite trend (see Fig. 16). When comparing the results of Fig(a),(c) and (d). It is obvious that the increase of w/c ratio at different
ages had similar effect on the content of C–S–H, Ca(OH)2 and MC. At 3days, the content of C–S–H, Ca(OH)2 kept unchanged with the
increase of w/c ratio, while with the increase of time, At 365 days. Mixes PC, CSP-10,CSP-20,CSP-30,CSP-40 witnessed the C–S–H
content increased by 7.1%,6.4%,6.1%,5.8% and 4.8% respectively. And the content of Ca(OH)2 increased by 3.6%, 3.4%, 3.1%,2.7%
and 2.3% respectively. As for the MC, which exist neither at early age of 3 days nor in PI mixes which containing no CSP, the increase of
w/c ratio result in the sharper increase in its content along with the increase of time. Which indicated that the increase of w/c ratio
could improve the hydration rate of the cementitious material. And longer the curing age is, more obvious this trend is.
Different from other three products mentioned above. The content of ettigate (AFt) decreased with the increase of W/C ratio. And
the decrease caused by the change of w/c ratio is increasingly significant along with the increase of time, especially for the specimen
with no CSP. The AFt content in mix with w/c ratio of 0.5 is 1.3% lower than the mix with w/c ratio of 0.3 at the age of 365 days, while

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Fig. 12. Hydration procedure of PC-CSP system.

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Fig. 13. Volume change of PI-CSP mix along with time.

at 3days, AFt content almost kept unchanged with the increase of w/c ratio.
Overall, as for the specimens containing CSP, the increase of w/c ratio would enhance the hydration, causing the decrease of AFt
content and the increase of C–S–H, Ca(OH)2, and Mc content. Apart from this, the content of these hydraulic products decrease with the
increase of CSP content,. This is mainly because of the filling effect and the comparable low hydraulic activity of CSP.

5.3. Effect of curing temperature

The content of C3A, AFT and MC of mixes with different content of CSP under different curing temperatures at different ages got
simulated through GEMS to investigate the effect of temperature on the hydration procedure. Thr result is shown in Fig. 17.
The content of C3A and AFt decreased while the content of Mc increased along with the increase of curing temperature through the
increase of curing age. For the specimens with no CSP, the content of C3A, which is one of the main clicker products, decreased by
1.5%, 1.0%, 0.6%, 0.4% and 0.1% respectively at the age of 3 days, 7days, 28days, 91days and 365days along with the increase of
temperature from 20 to 40 ◦ C, indicating that the hydration of C3A would be enhanced with the increase of temperature. The content of
AFt in mixes containing CSP went through slight decrease with the increase of temperature, while for the PI paste with pure PC, the
increase of temperature caused relatively more significant decrease in content of AFt, indicating that the higher temperature would
improve the transforming speed of AFt into AFm. Mc only existed in the mixes containing CSP, and content of which increased along
with the increase of temperature, while the enhancement of increasing temperature is most significant in the mix containing 10% of
CSP.
To summarize, the increase of curing temperature could enhance the hydration speed and increase the amount of hydraulic
products in PI-CSP systems, especially at the early ages. And the effect of temperature is more significant on the PI specimens con­
taining no CSP. This is mainly caused by the comparable lower reactivity of CSP. However, as for the content of Mc, the typical product
only existed along with CSP, the increase brought by warmer curing environment is more significant with the increase of CSP content.

6. Conclusion
This study investigated the hydraulic characteristics of cement paste containing CSP(Coral Sand Powder) using the experimental
and numerical methods. The influence of various factors including different content of CSP, water-cement ratio (w/c) and different
curing temperature on the mechanical properties, and hydraulic reaction through the time were investigated in this work. A ther­
modynamic model of hydration was established for the numerical simulation of portland cement-coral sand powder. The main con­
clusions are drawn as following:
(1) Low replacement of CSP (10%) had positive effect on the strength development of cement paste, compared with PC paste, while
with the increase of curing age and CSP content, the compressive and flexural strength generally decreases along with the
increase of CSP content and curing age.
(2) In the cement paste system, coral powder has a promoting effect on the early hydration of cement. It is because of its crystalline
nucleus effect in the process of cement hydration, and the hydration products C–S–H and CH are mainly attached and grown

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Fig. 14. Content of different elements in pore solution.

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Fig. 15. pH value of pore solution in CSP-PC specimens.

around the coral powder. However, in mixes with high content of CSP, the coral powder which has lower reactivity shows a
dilution effect along with the procedure of hydration reaction. The total heat release of hydration and the exothermic rate
decreased along with the increase of CSP content.
(3) In the cement paste system, the main hydration products includes Calcium hydrated silicate, Ca(OH) 2, monosulfate, calcaretite
and carbonate hydrated calcium aluminate. In PC paste containing no CSP, the quantity rank of hydraulic products from high to
low is Calcium hydrated silicate > Ca(OH)2>monosulfate > calcaretite. However, with the increase of CSP content from 10% to
40%, the conversion of calcaret to monosulfide hydrated aluminate is directly inhibited, the content of calcium alum stone
increased, the quantity rank of hydraulic products from high to low is Calcium hydrated silicate > Ca(OH) 2> calcaretite >
carbonate hydrated calcium aluminate.
(4) According to the comparison of Ca(OH)2 ‘content after hydration, the simulated results of GEMS agreed with the ones gotten
from the experiments, confirmed the reliability of the GEMS model.
(5) The increase of W/C ratio could improve the hydration rate of coral powder-Portland cement, Apart from this, the increase of
temperature would not change the species of main hydration products, but the hydration rate and product generation rate of
clinker increased in this procedure.

Credit author statement

Haiyan Ma.
Conceptualization, Methodology.
Haotian Fan*
Data curation, Writing- Original draft preparation, Methodology.
Hongfa Yu*
Methodology, Data curation, Visualization, Investigation writing- Reviewing and Editing.
Xinwen Peng.
Software, Validation.

Declaration of competing interest

The authors declare that they have no known competing financial interests or personal relationships that could have appeared to
influence the work reported in this paper.

Data availability

The data that has been used is confidential.

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Fig. 16. Hydraulic products of specimens of different w/c, content of CSP at different ages.

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Fig. 17. Hydraulic products of specimens with different temperature and content of CSP at different ages.

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Acknowedgement
The authors gratefully acknowledge the financial support received from the National Natural Science Foundation of China
(52078250, 51878350, 51678304), China.

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