Construction and Building Materials 126 (2016) 747–758

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Construction and Building Materials

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Improving the performance of reactive MgO cement-based concrete

mixes
N.T. Dung, C. Unluer ⇑
School of Civil and Environmental Engineering, Nanyang Technological University, 50 Nanyang Avenue, Singapore 639798, Singapore

h i g h l i g h t s

Quantity and morphology of carbonates determine the performance of MgO cement mixes.

Low hydration and high water demand of MgO limits strength gain in concrete mixes.

Inclusion of hydration agent enhanced MgO hydration, carbonation and strength gain.

Dispersant agent use reduced water demand, improved morphology and performance.

28 day strength of MgO concrete mixes containing these agents increased by over 50%.

a r t i c l e i n f o a b s t r a c t

Article history: Low hydration and high water demand of MgO limits strength gain in MgO cement-based formulations.
Received 24 February 2016 This study enhanced the microstructure and performance of MgO concrete mixes by increasing hydration
Received in revised form 9 September 2016 and lowering water demand via the introduction of hydration (HA) and dispersion (DA) agents. Hydration
Accepted 21 September 2016
and carbonation mechanisms were evaluated by isothermal calorimetry, TGA, XRD, FTIR and SEM. HA
increased MgO dissolution and brucite precipitation. DA reduced water content and resulted in denser
microstructures by increasing CO2 diffusion. Formation of dense carbonate networks with improved
Keywords:
morphologies resulted in 28-day strengths of 45 MPa, which were >50% higher than the control sample.
Reactive MgO
Hydration
Ó 2016 Elsevier Ltd. All rights reserved.
Carbonation
Compressive strength
Microstructure
Thermal analysis

1. Introduction The sequestration and permanent storage of CO2 in hydrated

Production of PC, which takes place at a rate of over 4
billion tonnes per year [1,2], is responsible for 5–10% of global
anthropogenic CO2 emissions [3], 2–3% of global primary energy
use [4] and a large consumption of natural resources. A new line of
research has emerged on the development of new cement formu-
lations with potentially lower carbon footprints, an example of
which is reactive magnesium oxide (MgO) cements. The use of
reactive MgO as a cement binder can provide some advantages
over PC due to its lower calcination temperatures (700–1000 vs.
1450 °C) [5,6] and strength gain associated with CO2 sequestration.
Moreover, MgO can be synthesized from seawater or brine
obtained as a waste at the end of the desalination process [5,7,8],
thereby reducing the consumption of natural resources.
⇑ Corresponding author.
E-mail address: ucise@ntu.edu.sg (C. Unluer).
MgO cement formulations leads to the production of hydrated
magnesium carbonates (HMCs) with different morphologies and
properties [9–12]. In these systems, HMCs are formed by the
hydration of MgO to form brucite (magnesium hydroxide, Mg
(OH)2), followed by its reaction with CO2. Some of the main
HMCs observed in carbonated MgO systems are nesquehonite
(MgCO33H2O), hydromagnesite (4MgCO3Mg(OH)24H2O) and
dypingite (4MgCO3Mg(OH)25H2O). Nesquehonite is prismatic
and forms star-like clusters, whereas hydromagnesite and dypin-
gite are composed of rounded rosette-like crystals.
Carbonation plays a critical role for the formation of HMCs,
which leads to hardening and strength gain in the prepared mixes.
The strength gain mechanism of reactive MgO formulations is
based on the increase in density associated with carbonation,
which reduces the overall pore volume (i.e. the formation of HMCs
causes a significant expansion and increases the solid volume
by a factor of 1.8–3.1); and microstructural evolution as the

http://dx.doi.org/10.1016/j.conbuildmat.2016.09.090
0950-0618/Ó 2016 Elsevier Ltd. All rights reserved.
748 N.T. Dung, C. Unluer / Construction and Building Materials 126 (2016) 747–758
morphology and the binding strength of the carbonate crystals
contribute to the network structure. The compact and interlocked
network-like structures established by the interconnected and
well-developed crystals control the overall performance [13,14].
As the carbonation and the associated formation of HMCs are pre-
ceded by the hydration of MgO at the end of which brucite is pro-
duced, the final performance and properties of the prepared
formulations primarily rely on the degree of hydration. The hydra-
tion of MgO includes the dissolution and precipitation processes
shown in Eqs. (1)–(4) [15]. The hydration process determines the
amount of brucite available to react with the diffused CO2, which
leads to the formation of HMCs and thereby strength gain. The
degree of MgO conversion to brucite under ambient conditions is
quite low, limiting the subsequent formation of carbonation
products. In addition to the slow dissolution of MgO [16,17], the
hydration and carbonation products precipitate on the surface of
MgO particles, which prevents further contact between the unhy-
drated MgO and available water for continuous hydration. Previous
studies have shown that hydration of reactive MgO is limited to
80% under ambient conditions, which is even lower under carbon-
ation [18–20], thereby resulting in an inefficient use of MgO as a bin-
der. Although the carbonation degree (i.e. conversion of brucite into
HMCs) of concrete mixes containing 10% reactive MgO as the main
binder was reported to reach up to 100%, the preceding hydration
reaction remained as low as 40–80%, depending on the mix design
and curing conditions [19]. This was mainly attributed to the incom-
plete dissolution (Eqs. (1)–(3)) and precipitation (Eq. (4)) processes.
MgO-alkaline oxide plays an electron donator role in water:
MgOðsÞ þ H2 O ! MgðOHÞþðsurfaceÞ þ OHðaqÞ

OH anions are adsorbed on the positively charged surface:
MgðOHÞþðsurfaceÞ þ OHðaqÞ ! MgOHþ  OHðsurfaceÞ
 2+
OH anions are desorbed from the surface, releasing Mg
OH ions into the solution:
MgOHþ  OHðsurfaceÞ ! Mg2þ 
ðaqÞ þ 2OHðaqÞ
Ion concentration reaches the solution supersaturation (pH
10.5), at which point the hydroxide starts to precipitate as brucite
on the oxide surface:

Mg2þ
ðaqÞ þ 2OHðaqÞ ! MgðOHÞ2ðsÞ
The main goal of this work is to increase the amount of CO2
sequestered and enhance the formation of HMCs and the overall
mechanical performance of the resulting formulations by improv-
ing the hydration of MgO. One way of achieving this is through
the introduction of a hydration agent (HA) and improvement of
curing conditions. Hydrochloric acid (HCl) is one of the most effec-
tive HAs reported in literature [21]. The presence of HCl increases
the H+ concentration, which in turn enhances the solubility of MgO
and the precipitation of Mg(OH)2 via the following steps [21,22]:
(i) Diffusion of the H+ ion through the liquid film at the liquid-
solid interface on the surface of the solid particles, (ii) surface
chemical reaction between MgO and H+ as shown in Eq. (5), (iii)
diffusion of liquid products from the interface through the film
to the bulk liquid and (iv) precipitation of Mg(OH)2 away from
the original particles. This alteration of the hydration mechanism
provides further space for the continuous hydration of MgO and
therefore increases the formation of Mg(OH)2.
MgOðsÞ þ 2HþðaqÞ ! Mg2þ
ðaqÞ þ H2 OðlÞ
Water to cement (w/c) ratio plays an important role in the
degree of hydration and carbonation of the prepared mixes
[9,19,23]. The water content influences the overall permeability,
which determines the rate of CO2 diffusion through the porous
systems. Although water provides a medium for carbonation to
take place, the excess water not only blocks the pores and hinders
CO2 diffusion (i.e. the diffusion coefficient of CO2 is
1390  108 m2/s in air, which is 104–105 less in water
[24,25]), but also results in a porous microstructure. An increase
in the initial water content results in an increase in porosity, which
decreases as hydration proceeds as the initial water is progres-
sively used to form the hydration products [26]. Lower w/c ratios
achieve high carbonation rates and fast strength development in
shorter curing durations. Understanding the role of water content
in strength development is particularly important for reactive
MgO cement formulations, whose water demand is higher than
corresponding PC mixes (i.e. the standard consistency of reactive
MgO is 0.6, whereas this value is 0.4 for PC) [19,27], generally
resulting in lower compressive strengths.
Therefore, in addition to increasing the hydration degree of the
prepared formulations, this work also aims to reduce their water
demand by introducing a dispersant agent (DA) that can defloccu-
late and improve the fluidity of the fresh mixes. Inorganic
phosphate salts such as sodium hexametaphosphate ((NaPO3)6,
referred to as NaHMP) are widely used as deflocculants in dispers-
ing natural raw materials [28,29]. NaHMP provides deflocculating
action through a mechanism that involves an increase of the
overall negative surface charge of molecules through its adsorption
as an anion, especially at particle edges. It can also dissolve the
flocculant Mg2+ by replacing it with Na+, therefore increasing the
thickness of the electrical double layer [28,30].
This study builds on the existing knowledge on the mechanisms
ð1Þ by which HA and DA contribute to the hydration process of differ-
ent materials and focuses on the role of these additives in facilitat-
ing the hydration and carbonation processes in the development of
ð2Þ reactive MgO-based concrete mixes with improved performance.
The carbonation process was enhanced by increasing the brucite
and available to react with CO2 through improving the preceding
hydration reaction via the use of a HA, while a denser microstruc-
ture was obtained by lowering the amount of water needed to
ð3Þ
achieve a desired consistency through the introduction of a DA.
After some preliminary trials based on previous studies involving
the use of different amounts of HCl and NaHMP [21,28,29], the
optimum concentrations of HCl (0.05 M) and NaHMP (1% of
cement by mass) were determined for their use as a HA and DA
ð4Þ in reactive MgO cement-based concrete mixes, respectively. Con-
crete samples subjected to natural (28 ± 2 °C, 80 ± 5% RH, ambient
CO2) and accelerated (30 °C, 80 ± 5% RH, 10% CO2) carbonation
were prepared to assess the influence of the HA and DA on the
mechanical performance and microstructure of the prepared for-
mulations under different CO2 concentrations (0.04% vs. 10%) over
a 28-day curing period. The effect of these two additives on the
hydration of MgO mixes was evaluated through Isothermal
Calorimetry. The degree of Mg(OH)2 and HMC formation was
calculated by thermogravimetric analysis (TGA). The performance
of the prepared formulations was analyzed by compressive strength
(CS) testing and water absorption measurements. Scanning electron
microscopy (SEM), Fourier transform infrared spectroscopy (FTIR)
and X-ray diffraction (XRD) were employed to investigate the
microstructure development and analyze the hydration and carbon-
ation products at the end of the curing process.
2. Materials and methodology
ð5Þ
2.1. Materials and mix preparation
The main cement binder used in this study was reactive MgO
(commercial name ‘‘calcined magnesite 92/200”) obtained from
 N.T. Dung, C. Unluer / Construction and Building Materials 126 (2016) 747–758
Richard Baker Harrison (UK). The chemical and physical properties
of MgO are shown in Table 1. HCl and NaHMP, both obtained from
VWR Singapore, were used as a HA and DA to improve the hydration
and performance of MgO as a binder, respectively. Gravel with a par-
ticle size of 4.7–9.5 mm was used in a saturated surface dry (SSD)
condition to form the aggregate profile in the prepared concrete
mixes.
The detailed mix designs are listed in Table 2. Before the casting
of concrete samples, the hydration mechanism of each mix was
studied individually by preparing corresponding paste composi-
tions containing HA and/or DA. The use of 1% DA reduced the water
demand of DA and HA.DA mixes from the original w/c of 0.6 to 0.5 to
achieve the same consistency as the control and HA mixes. DA was
first dissolved in water or the HA solution, which was then mixed
with the cement powder. These pastes were mixed with aggregates
at a cement/aggregate ratio of 0.67 for the preparation of concrete
samples.
50  50  50 mm cubic specimens were cast for the determina-
tion of water absorption and CS. Specimens were consolidated by
using a vibrating table and trowel finished, after which they were
kept in respective curing environments for 24 h until de-molding.
The demolded samples were subjected to two curing environments
for up to 28 days until testing: (i) natural (28 ± 2 °C, 80 ± 5% RH,
ambient CO2) and (ii) accelerated carbonation (30 °C, 80 ± 5% RH,
10% CO2) curing.
2.2. Methodology
2.2.1. Isothermal calorimetry
The heat flow and cumulative heat evolved due to the hydration
of each mixture were studied at 30 °C by an I-Cal 2000 High
Precision Calorimeter in accordance with ASTM C1702-15a [31].
To prepare the paste samples, MgO was added to water or HA solu-
tions, which were previously heated to 30 °C in order to produce
mixes at the same temperature as the measurement temperature.
The prepared mix was instantaneously placed into the isothermal
calorimeter channel to measure the heat of hydration.
2.2.2. Hydration degree
The hydration degree of MgO with and without HA and DA was
evaluated by TGA. Before the analysis, MgO pastes were stored in
acetone for at least 3 days to quench hydration and dried in a vac-
uum for at least 7 days to remove any remaining moisture. They
were then ground to pass through a 75 lm sieve in preparation for
TGA, which was conducted on a Perkin Elmer TGA 4000 equipment.
The samples were heated from 50 to 600 °C with a heating rate of
10 °C/min under nitrogen flow. The weight loss L (%) corresponding
to the dehydration of brucite was used to calculate the hydration
degree (HD) of MgO as shown in Eq. (6), where C is the actual MgO
content as a percentage of the total cement component. 40 and 18
are the molecular weights of MgO and H2O, respectively.
40
L 3.1. Isothermal calorimetry
HD ¼ 18
ð%Þ
ð1  0:01LÞC
2.2.3. Water absorption
The water absorption capacity was measured in accordance
with ASTM C642-13 [32]. The initial mass of the samples was
Table 1
Chemical composition and physical properties of MgO.
Chemical composition (%)
MgO SiO2 CaO R2O3*
MgO >91.5 2.0 1.6 1.0
*
R2O3: Al2O3 and Fe2O3.
749
recorded before they were immersed in a water tank. Their absorp-
tion mass was also measured when they reached a constant mass
under water, which reflected their water absorption capacity.
Water absorption (Wab) was calculated as a percentage of the ini-
tial mass as shown in Eq. (7), where mi and mab are the initial mass
and the absorption mass of samples after reaching a constant mass
when immersed in water, respectively.
ðmab  mi Þ
Wab ¼ ð%Þ ð7Þ
mi
2.2.4. Compressive strength
The CS of the prepared concrete mixes were measured by uni-
axial loading in triplicates at 3, 7, 14 and 28 days in accordance
with the specifications of ASTM C109/C109M-13 [33]. The equip-
ment used for this purpose was a Toni Technik Baustoffprüfsys-
teme machine, operated at a loading rate of 55 kN/min.
2.2.5. SEM, FTIR, XRD and TGA
Samples extracted from the cubes crushed during CS test were
stored in acetone for at least 3 days to stop hydration, followed by
vacuum drying for another 7 days in preparation for SEM, FTIR,
TGA and XRD. The dried samples were mounted onto aluminum
stubs using double-sided adhesive carbon disks and coated with
gold before SEM analysis, which was carried out with a Zeiss Evo
50 microscope to investigate the morphologies of the hydration
and carbonation products within the prepared samples. The
vacuum dried samples were ground down to pass through a
75 lm sieve in preparation for FTIR, TGA and XRD. FTIR spectra
of the samples were obtained by a Perkin Elmer FTIR Spectrometer
Spectrum GX. Spectra were recorded in transmittance mode from
2400 to 400 cm1 at a resolution of 1 cm1. TGA was conducted
on a Perkin Elmer TGA 4000 equipment from 50 to 950 °C with a
heating rate of 10 °C/min under nitrogen flow.
XRD was recorded on a Philips PW 1800 spectrometer using Cu
Ka radiation (40 kV, 30 mA) with a scanning rate of 0.04° 2h/step
from 5 to 80° 2h. The RIR technique [34–36] was applied for the
quantitative analysis of the phases present by making use of a
standard phase with a known proportion, whose integrated inten-
sity was compared to that of the phase of interest. The internal
standard used for quantification purposes was fluorite (CaF2)
included at 5 wt.% [37]. Calibration curves for MgO and Mg(OH)2,
the two main components used for quantitative analysis, are
straight lines through the origin i.e. y = kx, where x is the RIR of
the phase analyzed and y is the weight fraction of the component
investigated. The value of k is 0.2886 for MgO and 0.3651 for Mg
(OH)2. The RIR was acquired by dividing the integrated intensity
of the strongest line of the phase with that of the standard.
3. Results
ð6Þ
Fig. 1(a) and (b) show the heat flow and the cumulative heat of
all pastes over 72 h of hydration, respectively. As seen in Fig. 1(a),
the dissolution of MgO and the formation of brucite resulted in an
early exothermic peak in the control and HA mixes within the first
few hours of mixing. The inclusion of HA led to a higher peak than
Physical properties
K2O Na2O LOI Specific gravity (g/cm3) Specific surface area (m2/g)
– – 4.0 3.0 16.3
750 N.T. Dung, C. Unluer / Construction and Building Materials 126 (2016) 747–758

Table 2
Composition of the mixes prepared for the investigation of mechanical performance and microstructural development under different conditions.

Mix number Mix label W/C NaHMP (%) Cement/aggregate HA solution

Type Concentration (M)
1 Control 0.6 0 0.67 H2O –
2 HA 0.6 0 HCl 0.05
3 DA 0.5 1 H2O –
4 HA.DA 0.5 1 HCl 0.05

the control mix. The inclusion of DA in HA.DA and DA mixes led to
a dormant period of 10–15 h, followed by a lower hydration peak.
A small peak associated with the dissolution of MgO was followed
by the dormant period, after which a broader exothermic peak
attributed to the precipitation of brucite was observed at 24
and 38 h for HA.DA and DA mixes, respectively. The differences
in the hydration behaviours of these mixes were related to the
presence of DA, which modified the hydration rate and precipita-
12
(a)
9 3.2. Hydration degree
Heat flow (mW/g)
tion of brucite. The significantly higher exothermic peak obtained
by the HA mix when compared to the control and DA mixes con-
firmed the role of HA in enhancing the hydration of MgO.
The cumulative heat curves in Fig. 1(b) clearly indicate an
increased degree of hydration with the inclusion of HA, while the
inclusion of DA had an opposite effect. This could be attributed
to the deflocculating effect of DA that delayed the hydration of
MgO and the subsequent precipitation of brucite. The highest
degree of hydration was revealed by the HA mix, whereas the DA
mix led to the lowest amongst all mixes. When compared to the
DA mix, the inclusion of HCl as the HA in the HA.DA mix increased
hydration by lowering the pH of the solution and enhancing the
Control solubility of MgO for the formation of Mg(OH)2.
HA
DA

HA.DA Fig. 2 illustrates the hydration degree of all samples up to

14 days under sealed conditions (i.e. to prevent carbonation). The
6 hydration degree values, which were consistent with the isother-
mal calorimetry results, increased with age for all samples. The
use of HA resulted in an obvious increase in the hydration degree
of the HA and HA.DA mixes. When compared to the control mix,
whose hydration degree was limited to 49%, the use of HCl in
3 the HA mix enhanced the hydration process and increased the
hydration degree to 53% at the end of 3 days. A similar trend
was observed at 14 days, at which the hydration degree of the con-
trol mix was increased from 68% to 72% via the inclusion of HA.
0 Similarly, the 3-day hydration degree of the DA mix increased from
49% to 54% in the HA.DA mix. Although a slower hydration was
0 20 40 60 80
observed in the earlier ages, the use of DA revealed a similar hydra-
Time (h) tion degree as the control mix at 3 and 14 days. Mixes HA and HA.

500

(b)
400
Cumulative heat (J/g)

300

200
Control
HA
100
DA
HA.DA
0
0 20 40 60 80
Time (h)
Fig. 1. Isothermal calorimetry results of all samples showing the (a) heat flow and
(b) cumulative heat. Fig. 2. Hydration degree results of all samples.
 N.T. Dung, C. Unluer / Construction and Building Materials 126 (2016) 747–758 751

Table 3
Water absorption of samples after 14 and 28 days of curing.

Mix label Ambient curing Accelerated curing

(wt.%) (wt.%)
14 days 28 days 14 days 28 days
Control 11.73 11.19 5.89 4.36
HA 11.45 10.79 5.17 3.69
DA 10.49 10.44 3.72 2.54
HA.DA 9.64 8.62 4.43 3.60

DA achieved the highest hydration degrees amongst all mixes at

the end of 14 days, revealing figures as high as 72%.

3.3. Water absorption

The water absorption of all mixes after 14 and 28 days under

ambient and accelerated carbonation conditions is presented in
Table 3. In both curing conditions, HA, DA and HA.DA mixes
absorbed less water than the control mix. This was attributed to
the lower water demands and denser microstructures of DA and
HA.DA mixes, along with the higher hydration degree of the HA
mix. The increased hydration degree enhanced the carbonation
process and the associated formation of HMCs, which led to a
dense microstructure. The effective role of HA and DA in reducing
the amount of pores available for water absorption was more obvi-
ous under accelerated carbonation than ambient curing due to the
increased extent of carbonation in the former. In addition to the
increased CO2 concentrations, longer curing periods generally led
to lower water absorption values as hydration and carbonation
proceeded further with time, increasing the overall density.
The water absorption of the control mix was recorded as 11.7%
and 11.2% after 14 and 28 days of ambient curing, respectively. The
inclusion of HA reduced the water absorption at 28 days by 4%,
resulting in a value of 10.8%. Larger reductions of 7% and 23%,
resulting in water absorption values of 10.4% and 8.6% were
recorded in DA and HA.DA mixes, respectively. The water absorp-
tion of the control mix reduced to 5.9% and 4.4% after 14 and
28 days of accelerated carbonation, respectively. The inclusion of
HA led to a reduction in these values by up to 12% and 15%,
resulting in 14- and 28-day values of 5.2% and 3.7%, respectively.
The use of DA resulted in even further reductions of 37% and
41% when compared to the control mix, resulting in absorption
values of 3.7% and 2.5% after 14 and 28 days, respectively. The
simultaneous inclusion of HA and DA in the HA.DA mix led to Fig. 3. Compressive strength of all samples under (a) ambient and (b) accelerated
higher absorption values than the use of DA alone (DA mix) and carbonation.
lower values than the use of HA alone (HA mix), as expected. This
was attributed to the reduction in the amount of mixing water
with the introduction of DA and the increased formation of brucite 14 days. The inclusion of HA and DA at the same time (HA.DA
available for carbonation due to the presence of HA. Therefore, mix) led to >7 MPa at 14 days, satisfying the minimum strength
both additives facilitated the enhanced formation of a dense car- requirement for masonry blocks without the need for any acceler-
bonate network, which improved the performance of the prepared ated carbonation [38]. The strength of this mix increased up to
mixes. 8.5 MPa at 28 days, while the control mix revealed much lower
strengths of 4.0 MPa.
3.4. Compressive strength Samples subjected to accelerated carbonation led to much
faster strength development and higher strength results than those
Fig. 3(a) and (b) show the CS of concrete mixes cured under cured under ambient conditions due to the rapid and more exten-
ambient and accelerated carbonation conditions, respectively. sive formation of HMCs under higher CO2 concentrations (0.04% vs.
When compared to the control mix, mixes containing HA and DA 10%). When compared to the control mix, the inclusion of HA and/
indicated a faster strength gain under both conditions. As shown or DA led to a significant increase in the strength of all mixes. As
in Fig. 3(a), the strength of the control mix under ambient condi- seen in Fig. 3(b), the DA mix gained a strength of over 8 MPa in
tions was 2.5 MPa at 3 days, which slightly increased to only 3 days, at which the strength of the control mix was limited
2.9 MPa at 14 days. A similar trend was observed in HA and DA to 3 MPa. Mixes HA, HA.DA and DA produced strengths 35, 105
mixes that reached up to 3.4 MPa at 3 days. However, unlike the and 135% higher than the control mix (15 MPa) at 14 days and
control mix, these mixes indicated a faster strength gain from achieved 20, 31 and 35 MPa, respectively. A similar trend was
3 days onwards and achieved strengths as high as 6.2 MPa at obtained at 28 days, during which the control mix revealed
752 N.T. Dung, C. Unluer / Construction and Building Materials 126 (2016) 747–758

28 MPa, whereas mixes HA, HA.DA and DA achieved 30, 43 and
45 MPa, respectively.
The use of HA and DA separately or simultaneously led to an
improvement in the mechanical performance of the control mix
at all times under both curing conditions. The contribution of HA
to strength gain could be attributed to the enhanced solubility of
MgO and increased formation of brucite available for carbonation,
clearly shown by the isothermal calorimetry and hydration degree
results. The inclusion of DA also contributed to strength gain by
lowering the amount of mixing water needed to achieve the
desired consistency and enabling the formation of a denser
microstructure, as proven by the water absorption results pre-
sented earlier in Table 3.

3.5. Microstructural analysis

Fig. 4 presents the microstructures of all mixes after 14 days of

ambient curing. Unlike previous studies performed on MgO
cement mixes subjected to ambient curing, the formation of vari-
ous HMCs were clearly observed after only 14 days under ambient
curing conditions. This was more obvious for mixes involving the
use of HA and DA. Disk-like formation of hydromagnesite/
dypingite (diameter 0.2 lm, thickness <0.1 lm) was observed
after the carbonation of the control mix under ambient conditions,
as shown in Fig. 4(a). Clusters of much larger hydromagnesite/
dypingite (diameter 1.5–2 lm, thickness <0.1 lm) along with
un-carbonated brucite disks (diameter 1.5 lm, thickness
0.1 lm) was observed in the HA mix shown in Fig. 4(b). The
abundant formation of hydromagnesite/dypingite (diameter
1–1.5 lm, thickness <0.1 lm) that agglomerated into a rosette-
like form mixed with needle-like nesquehonite (diameter 0.5–
1 lm, length >5 lm) led to the dense microstructure of the DA
mix shown in Fig. 4(c). The inclusion of HA and DA in the same
mix revealed the formation of clusters of hydromagnesite/
dypingite (diameter 1 lm, thickness <0.1 lm) amongst an exten-
sive matrix of un-carbonated brucite disks (diameter 5 lm, thick-
ness 0.2 lm) in the HA.DA mix shown in Fig. 4(d). When
compared to the control mix, mixes incorporating HA and/or DA
enlarged the crystal sizes of HMCs by up to 5–10 times, explaining
their higher CS and lower water absorption values.
The microstructures of all mixes after 14 days of accelerated
carbonation are presented in Fig. 5. When compared to those under
ambient curing, samples subjected to accelerated carbonation
revealed much denser microstructures composed of a more
extensive formation of HCMs. In addition to the higher quantities,
the morphologies of the HMCs formed under accelerated carbona-
tion were significantly larger than those under ambient curing.
Moreover, an extensive formation of nesquehonite was observed
in the HA and HA.DA mixes under accelerated carbonation as
opposed to the un-carbonated brucite domination observed under
ambient curing. Therefore, the use of HA and DA in MgO mixes
subjected to accelerated carbonation resulted in the co-existence
of hydromagnesite/dypingite and nesquehonite rather than the
sparsely formed hydromagnesite/dypingite revealed by the control
mix.
The formation of hydromagnesite/dypingite (diameter 1 lm,
thickness <0.1 lm) was observed in the control mix after 14 days
of carbonation, as seen in Fig. 5(a). The accelerated carbonation
of the HA mix led to the formation of large nesquehonite needles
(diameter 1 lm, length >5 lm) accompanied by hydromagne-
site/dypingite disks (diameter 1–4 lm, thickness 0.1 lm). A Fig. 4. SEM images after 14 days under ambient carbonation of samples: (a)
similar morphology was observed after the carbonation of the DA Control, (b) HA, (c) DA and (d) HA.DA.
mix with nesquehonite (diameter 0.5 lm) and hydromagnesite/
dypingite (diameter 1 lm, thickness <0.1 lm) with smaller sizes
forming, albeit forming a dense microstructure. This dense measurements, in which the DA mix revealed favorable results
structure was in line with the strength and water absorption when compared to the others. An extensive formation of
 N.T. Dung, C. Unluer / Construction and Building Materials 126 (2016) 747–758
Fig. 5. SEM images after 14 days under accelerated carbonation of samples: (a)
Control, (b) HA, (c) DA and (d) HA.DA.
hydromagnesite/dypingite disks (diameter up to 4 lm, thickness
0.1 lm) covered by sheets of long nesquehonite needles (diame-
ter 0.5–1 lm, length 8–9 lm) after the carbonation of the HA.
753
DA mix shown in Fig. 5(d) revealed the co-existence of these HMCs
within the same mix along with a possible transition from one
form to another, depending on the conditions. Under accelerated
carbonation conditions, mixes incorporating HA and/or DA not
only formed larger HMC crystals, but also led to denser microstruc-
tures in which hydromagnesite/dypingite was firmly mixed with
nesquehonite, explaining their higher CS and lower water absorp-
tion values when compared to the control mix.
3.6. FTIR
The FTIR spectra of all mixes after 14 days of curing under ambi-
ent and accelerated carbonation conditions are presented in Fig. 6
(a) and (b), respectively. When compared to ambient curing, car-
bonation bands with much higher intensities were obtained after
accelerated carbonation, which was consistent with the CS results
and microstructure observations. Regardless of the curing condi-
tions, the inclusion of HA and DA led to larger absorption bands
than the control mix, suggesting higher amounts of HMC formation
and confirming the increase in strength with the introduction of
HA and DA.
In the case of ambient curing shown in Fig. 6(a), the control mix
showed a weak absorption band at 1447 cm1, assigned to the
presence of CO2 3 [39]. The HA mix showed a shoulder at
1447 cm1 along with an absorption band at 1483 cm1 assigned
to HMCs [40]. A CO2 3 band at 1447 cm1 was also observed in
the DA mix, whereas this was accompanied with a shoulder at
1545 cm1 in the HA.DA mix, assigned to the formation of HMCs
[39,40]. In contrast to the control mix, the incorporation of HA
and DA in MgO mixes resulted in larger absorption bands corre-
sponding to CO2 3 . This was consistent with the higher amounts
of HMC formation within these mixes than the control mix,
explaining their improved mechanical performance even under
ambient conditions.
The accelerated carbonation results shown in Fig. 6(b), revealed
a broad band between 1506 and 1414 cm1 for the control mix,
which was slightly shifted and split into three different shoulders
between 1545 and 1414 cm1 for the HA and DA mixes. The com-
bination of HA and DA shifted this broad band to 1483 and
1414 cm1 for the HA.DA mix. The major difference between the
results obtained under ambient and accelerated carbonation was
the significant increase in the intensity of this broad band in the
latter case, corresponding to the extensive formation of HMCs
under increased CO2 concentrations. These broad bands were
ascribed to CO2 3 within hydromagnesite/dypingite and nesque-
honite [39–41], which contributed to the development of
microstructural strength through their dense formation. The inclu-
sion of HA and DA showed a vibration absorption from 1800 to
1600 cm1 in HA, DA and HA.DA mixes, attributed to the formation
of HMCs [40,42,43]. The additional shoulder observed at
850 cm1 within these mixes also referred to the presence of
CO2
3 [40,41], which was in agreement with the microstructural
observations. In addition to the higher intensities of the CO2 3
bands, the extensive HMCs formation along with other HMCs
observed in HA, DA and HA.DA mixes can explain the higher
strength results obtained when compared to the control mix. This
was further enhanced in the DA and HA.DA mixes, whose w/c
ratios were reduced to compensate for the inclusion of DA, which
further contributed to strength gain.
3.7. XRD
XRD patterns of all mixes after 14 days of curing under ambient
and accelerated carbonation conditions are depicted in Fig. 7
(a) and (b), respectively. Amongst some minor peaks of other HMCs,
peaks of nesquehonite, artinite, dypingite and hydromagnesite were
754 N.T. Dung, C. Unluer / Construction and Building Materials 126 (2016) 747–758

(a) MgO, but also enabled the reaction with the formed brucite to form
a range of HMCs. As a result of these reactions, mixes subjected to
accelerated carbonation showed smaller unhydrated MgO and

1447
uncarbonated brucite contents than the corresponding mixes
under ambient conditions. Mixes including HA and DA resulted
in significantly smaller residual MgO contents than the control

1483
mix. The unhydrated MgO content of the control mix subjected
accelerated carbonation for 14 days was 31%. With the introduc-
tion of HA, this number was significantly reduced to 22% and
25% for HA and HA.DA mixes, respectively. The use of DA in
1447

MgO mixes also led to improved hydration when compared to

the control mix, reporting an unhydrated MgO content of 28%.
These low residual MgO contents were reflected as increased
brucite contents within HA, HA.DA and DA mixes, whose brucite
1545

content ranged between 45% and 50%. The presence of uncarbon-

1447

ated brucite highlights the unutilized potential of these mixes in

achieving even higher strengths than those reported in this study
2400 2000 1600 1200 800 400 (i.e. up to 45 MPa). These strengths can be further increased with
-1 optimized mix designs and curing conditions.
Wavenumber (cm )
3.8. TGA
(b)
The weight loss and heat flow data of all mixes after 14 days of
curing under ambient and accelerated carbonation conditions
1506
1414

measured by TGA are presented in Fig. 8(a) and (b), respectively.

In addition to a strong endothermic peak at 380 °C and a broader
beak at 700 °C clearly visible in both figures, mixes exposed to
1545

accelerated carbonation indicated two endothermic peaks at

1414

120 and 220 °C, as seen in Fig. 8(b). The weight losses associ-
ated with the decomposition of HA or DA that resulted in minor
weight losses were accompanied by three main decomposition
1414

steps in agreement with pervious literature [44–50]. These stages

are summarized in Table 5 and identified as:

(i) 50–300 °C: Dehydration of water bonded to HMCs (e.g.

1483
1414

nesquehonite, hydromagnesite and dypingite) [44,46–50].

(ii) 300–500 °C: Dehydroxylation of some HMCs (e.g. hydro-
magnesite and dypingite), decarbonation of some HMCs
2400 2000 1600 1200 800 400 (e.g. nesquehonite) and decomposition of uncarbonated
-1 brucite [45–47,49,50].
Wavenumber (cm )
(iii) 500–900 °C: Decarbonation of HMCs (e.g. nesquehonite,
DA
hydromagnesite and dypingite) [47,50].
Control

HA HA.DA
Fig. 6. FTIR spectra of all samples under (a) ambient and (b) accelerated
carbonation.
observed. The presence of residual MgO and brucite, whose quanti-
ties were calculated and listed in Table 4, were also observed in both
curing conditions.
Under ambient curing, the control mix revealed a higher resid-
ual MgO content (34%) corresponding to a lower brucite forma-
tion than the HA mix (32%), but lower MgO contents than those
of the DA (37%) and HA.DA (36%) mixes. This was consistent
with the hydration patterns shown by the isothermal calorimetry
analysis and proved the active role of HA in improving the conver-
sion of MgO into Mg(OH)2. Carbonation was not as extensive in
ambient curing as it was in accelerated carbonation conditions,
therefore revealing uncarbonated brucite contents as high as 55–
58% for all mixes. The increased hydration degree of the HA mix
was reflected as higher brucite content available for carbonation
than the control mix (58% vs. 56%). Mixes DA and HA.DA had
similar uncarbonated brucite contents as the control mix.
The increased CO2 concentration applied under accelerated car-
bonation not only created a suitable media for the hydration of
Table 6 summarizes the weight loss of all mixes at each step
along with the total weight loss. The weight loss due to the decom-
position of HMCs within each sample was calculated by subtract-
ing the weight loss of brucite, whose content was determined by
XRD analysis (Table 4), from the total weight loss. The findings
listed in Table 6 indicate that a majority of the weight loss is
observed in the 300–500 °C temperature range, which is associated
with 3 main reactions attributed to the: (i) dehydroxylation of
hydromagnesite and dypingite, (ii) decarbonation of nesquehonite
and (iii) decomposition of uncarbonated brucite. Regardless of the
curing conditions, samples containing HA and DA revealed higher
HMC contents than the control mix. This was mainly because the
inclusion of HA increased the amount of brucite available for car-
bonation, which led to the enhanced formation of HMCs. A similar
effect was observed in the DA mix and was attributed to the direct
carbonation of the Mg2+ solution, which took place more readily
than the carbonation of brucite crystals, whose precipitation was
delayed due to the use of DA. This could be explained by the car-
bonation mechanism of brucite, which initiated on the outer edges
and led to the formation of HMCs that covered the uncarbonated
brucite, hindering the further diffusion of CO2 within the uncar-
bonated brucite system. On the other hand, the diffused CO2 could
directly dissolve and homogenously react with the Mg2+ solution
 N.T. Dung, C. Unluer / Construction and Building Materials 126 (2016) 747–758 755

Fig. 7. XRD patterns of all samples after 14 days under (a) ambient and (b) accelerated carbonation.

Table 4 within the DA mix. This mechanism led to an increased formation

MgO and Mg(OH)2 contents obtained by XRD after 14 days of curing. of HMCs when compared to the control mix.
Mix label Ambient curing (wt.%) Accelerated curing (wt.%) Under ambient conditions, the HA.DA mix revealed the highest
total weight loss (26%) along with the weight loss corresponding
MgO Mg(OH)2 MgO Mg(OH)2
to the presence of HMCs (9%), which can explain the highest 14-
Control 34.23 56.35 31.18 42.14
day strength results (>7 MPa) obtained by this mix. The HA and DA
HA 32.32 58.48 21.84 50.45
DA 36.74 55.27 27.62 44.88 mixes also outperformed the control mix by revealing higher
HA.DA 35.51 56.80 25.11 46.36 weight losses due to the decomposition of HMCs and in total. These
results were in line with the CS values reported by each mix, which

Table 5
Thermal decomposition of hydrate and carbonate phases within MgO cement formulations.

Phase Decomposition reactions

50–300 °C 300–500 °C 500–900 °C
Brucite Mg(OH)2 – Mg(OH)2 ? MgO + H2O –
Nesquehonite MgCO33H2O MgCO33H2O ? MgCO3 + 3H2O MgCO3 ? MgO + CO2 MgCO3 ? MgO + CO2
Hydromagnesite 4MgCO3Mg(OH)24H2O 4MgCO3Mg(OH)24H2O ? 4MgCO3Mg(OH)2 + 4H2O 4MgCO3Mg(OH)2 ? 4MgCO3 + MgO + H2O MgCO3 ? MgO + CO2
Dypingite 4MgCO3Mg(OH)25H2O 4MgCO3Mg(OH)25H2O ? 4MgCO3Mg(OH)2 + 5H2O 4MgCO3Mg(OH)2 ? 4MgCO3 + MgO + H2O MgCO3 ? MgO + CO2
756 N.T. Dung, C. Unluer / Construction and Building Materials 126 (2016) 747–758

HMCs under high CO2 concentrations (10 vs. 0.04%) and the contri-
bution of these HMCs to the overall strength gain. When compared
to the control mix, the use of HA and/or DA increased the amount
of HMCs by up to 15% and 23% within mixes cured under ambient
and accelerated carbonation conditions, respectively. The HA
and/or DA included within MgO cement formulations demon-
strated a more influential role in the strength gain of mixes under
accelerated carbonation as opposed to natural curing. This was
because accelerated carbonation conditions enabled the effective
utilization of the increased amount of brucite produced or the
direct carbonation of the Mg2+ solution due to the introduction
of these additives. This reaction with CO2 resulted in the dense
formation of a strong carbonate network that determined in the
overall mechanical performance of each mix.

4. Discussion

This study demonstrated the separate and simultaneous use of

Fig. 8. Weight loss and heat flow of all samples after 14 days under (a) ambient and
(b) accelerated carbonation.
were higher than the control mix. A much more obvious difference
in the weight losses obtained by TGA was present in the case of
accelerated carbonation, in which the HMC content of the control
mix was limited to 19% with a total weight loss of 32%. The
inclusion of DA and HA increased the HMC content to 22–23%,
whereas higher total weight losses of 36–39% were also obtained.
The weight losses due to the decomposition of carbonation
products within the control mix and mixes containing HA and/or
DA subjected to accelerated carbonation were 153% and 166–
207% higher than the corresponding samples cured under ambient
conditions, respectively. This proves the extensive formation of
HA and DA in improving the microstructure and mechanical per-
formance of reactive MgO cement-based concrete formulations
under ambient and accelerated carbonation conditions. The inclu-
sion of HA increased the amount of brucite available for carbona-
tion by enhancing the dissolution of MgO and precipitation of
brucite, as demonstrated by isothermal calorimetry and hydration
degree results. The extra brucite available led to a more extensive
carbonation, thereby improving the mechanical performance of
samples. The use of DA also resulted in a denser microstructure
and higher carbonation degree than the control mix by directly
stimulating carbonation and strength gain through reduced water
contents. The simultaneous inclusion of HA and DA significantly
improved the morphology as well as the performance of samples
under both conditions.
The inclusion of HA increased the hydration degree of the con-
trol mix by 6–7% by enhancing the dissolution of MgO. The exten-
sive brucite formation increased the amount of carbonation and
HMCs, which contributed to the improved performance of the HA
mix. The FTIR results demonstrated CO2 3 bands with higher inten-
sities after the ambient and accelerated curing of the HA mix when
compared to the control mix. XRD and TGA results also confirmed
that the inclusion of HA not only increased brucite formation, but
also enhanced the HMC content, which was up to 23% higher than
the control mix. The inclusion of HAs not only improved the
amount of HMCs but also their morphology by resulting in HMC
crystals up to 10 times larger than those of the control mix. The
microstructure of the HA mix subjected to accelerated carbonation
revealed elongated nesquehonite needles blended with an exten-
sive formation of hydromagnesite/dypingite disks, which was
more advantageous than the sparsely formed hydromagnesite/
dypingite exposed by the control mix. The extensive formation of
HMCs in the HA mix resulted in denser microstructures and up
to 12% lower water absorption values, which translated into
114% and 35% higher compressive strengths than the control

Table 6
Weight loss of mixes obtained by TGA after 14 days of curing.

Curing condition Mix label Weight loss (wt.%)

50–300 °C 300–500 °C 500–900 °C Mg(OH)2 HMCs Total
Ambient curing Control 1.83 18.73 4.30 17.49 7.37 24.86
HA 1.70 19.66 4.25 18.15 7.46 25.61
DA 2.55 18.44 4.03 17.15 7.87 25.02
HA.DA 3.00 18.91 4.23 17.63 8.51 26.14
Accelerated curing Control 4.40 22.85 4.49 13.08 18.66 31.74
HA 8.44 25.78 4.33 15.66 22.89 38.55
DA 7.5 23.77 4.37 13.93 21.71 35.64
HA.DA 8.13 24.69 4.24 14.39 22.67 37.06
 N.T. Dung, C. Unluer / Construction and Building Materials 126 (2016) 747–758
mix after 14 days under ambient and accelerated carbonation con-
ditions, respectively.
The deflocculating effect of DA delayed the hydration of MgO
and the subsequent precipitation of brucite, leading to lower
hydration degrees at early ages (i.e. 63 days), which increased in
later ages. This delayed precipitation of brucite may have enabled
the direct carbonation of the Mg2+ solution, which can take place
more readily than the carbonation of brucite crystals. This was
explained by the hindering of the continuous diffusion of CO2
and carbonation of brucite by the formation of HMCs on the uncar-
bonated brucite surfaces. Alternatively, the diffused CO2 could
directly dissolve and react with the Mg2+ solution available within
the DA mix. Another positive effect of the introduction of DA on
carbonation was the reduced water content needed to achieve a
certain workability, which enabled a denser microstructure and
faster diffusion of CO2 within the pore system when compared to
a system relatively more saturated with water. Considering that
the diffusion coefficient of CO2 is 16 mm2/s in air and
0.0016 mm2/s in water [51], the transport of CO2 through a satu-
rated pore is much slower. The lower initial water content of the
DA mix therefore led to the formation of a higher amount of HMCs
than the control mix under both ambient and accelerated carbon-
ation conditions. CO2 3 bands with higher intensities revealed by
FTIR, supported by the 16% higher HMC contents obtained by
XRD and TGA analyses, confirmed the reasoning behind the out-
standing performance of the DA mix, especially under accelerated
carbonation curing. The dense microstructure facilitated by the
extensive formation of HMCs within the DA mix was supported
by the improvement of the morphology of the hydromagnesite/
dypingite crystals, which were not only larger in size and more
densely packed than those of the control mix, but also co-existed
with nesquehonite. The simultaneous formation of these HMCs
observed under both curing conditions led to the formation of a
strong carbonate network that contributed to the overall mechan-
ical performance of the DA mix. These improvements translated
into 37% reduced water absorption as well as 65% and 135%
increase in the compressive strength when compared to the con-
trol mix after 14 days under ambient and accelerated carbonation
conditions, respectively.
The simultaneous use of HA and DA in MgO cement formula-
tions achieved the highest HMC content, lowest water absorption
and highest compressive strength under ambient curing albeit its
lower hydration degree than that of the HA mix. A similar trend
was obtained under accelerated carbonation conditions, in which
mixes HA.DA and DA outperformed all others in terms of mechan-
ical performance. The strength results clearly indicate that the sole
use of HA is particularly beneficial under ambient curing condi-
tions during which the available water content within the mix
and the surrounding environment can have a large influence on
the continuation of hydration and the subsequent carbonation
reactions. The fast hydration facilitated by the inclusion of HA
can eliminate any potential reductions in strength caused by fluc-
tuations in the ambient curing conditions. This was less influential
under accelerated carbonation conditions during which carbona-
tion takes place at a much faster rate due to the increased CO2
concentrations provided. In this scenario, the provision of a dense
microstructure enabled by the lower initial water contents and the
faster diffusion of CO2 within the relatively drier pore structure
provided by the inclusion of DA has a direct influence on the over-
all strength gain. This is also supported by the improved morphol-
ogy of carbonates observed in mixes including HA and DA.
5. Conclusions
The main goal of this study was to improve the carbonation,
associated microstructure and mechanical performance of reactive
757
MgO cement-based concrete mixes by enhancing the preceding
hydration process for the formation of a higher amount of brucite
available for carbonation. HCl was used as the HA to increase the
conversion of MgO into brucite, which then reacted with CO2 to
form a range of strength providing carbonate phases. NaHMP
was included as the DA in the initial mix design to reduce the
overall water demand and produce denser microstructures. The
hydration and carbonation mechanisms were investigated under
ambient and accelerated carbonation conditions.
The findings of this study indicated the significant potential of
reactive MgO cement-based concrete formulations in achieving
high strengths within a few days by enhancing the hydration and
microstructure of the resulting carbonate system. The introduction
of HA into MgO mixes improved the rate and degree of MgO hydra-
tion, which in turn increased the amount of brucite available for
carbonation. The use of DA delayed the precipitation of brucite,
increased the diffusion rate of CO2 and facilitated direct carbona-
tion by enabling the use of initial lower water contents. As a result,
the inclusion of HA and/or DA in carbonated MgO cement formula-
tions resulted in the formation of a denser carbonate network
composed of a higher amount of HMCs with larger sizes than the
control mix. This improvement in morphology translated into
improved mechanical performance by reaching strengths as high
as 8.5 MPa and 45 MPa after 28 days under ambient and acceler-
ated carbonation conditions, respectively. These were 115% and
58% higher than the corresponding strengths of the control mix.
A similar trend was observed in the water absorption results, in
which mixes involving the use of HA and/or DA resulted in
absorption values as low as 9% and 3% after 28 days of ambient
and accelerated carbonation, respectively. These were 23% and
42% lower than the corresponding values of the control mix.
Acknowledgement
The authors would like to acknowledge the financial support
from the Singapore MOE Academic Research Fund Tier 1 (RG
113/14) for the completion of this research project.
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