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Cement and Concrete Research 57 (2014) 1–12

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Cement and Concrete Research


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MgO expansive cement and concrete in China: Past, present and future
Liwu Mo a,⁎, Min Deng a,b, Mingshu Tang a, Abir Al-Tabbaa c
a
College of Materials Science and Engineering, Nanjing University of Technology, No. 5 Xinmofan Road, Nanjing, Jiangsu 210009, China
b
State Laboratory of Materials-Oriented Chemical Engineering, Nanjing 210009, China
c
Department of Engineering, University of Cambridge, Trumpington Street, Cambridge CB2 1PZ, UK

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

Article history: Uniquely, China employs MgO already contained in cement clinker or as an expansive additive to compensate for
Received 8 May 2013 the thermal shrinkage of mass concrete, particularly dam concrete, with almost 40 years' experience in both
Accepted 15 December 2013 research activities and industrial applications. Compensating shrinkage with expansion produced by MgO has
been proved to effectively prevent thermal cracking of mass concrete, and reduce the cost of temperature control
Keywords:
measures and speed up the construction process. Moreover, the expansion properties of MgO could be designed
Hydration (A)
Characterization (B)
flexibly, through adjusting its microstructure by changing the calcination conditions (calcining temperature and
Expansion (C) residence time). The collective knowledge and experience of MgO expansive cement and concrete is worthy
MgO (D) of sharing with relevant engineers and researchers globally but dissemination has been hindered as most of
Concrete (E) the relevant literature is published in Chinese. This paper reviews the history, state-of-the-art progress and future
research needs in the field of MgO expansive cement and concrete.
© 2013 Elsevier Ltd. All rights reserved.

Contents

1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1
2. Brief history of MgO expansive cement and concrete . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2
3. Hydration and expansion of MgO in cementitious materials . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2
3.1. Hydration and expansion of dead burnt periclase in cement clinker . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2
3.2. Hydration and expansion of MEA . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3
3.3. Factors influencing the hydration and expansion of MgO . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5
4. Performance of MgO concrete . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 6
4.1. Expansion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 6
4.2. Mechanical properties and durability . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 7
4.3. Soundness . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 7
5. Manufacture of MEA . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 8
5.1. Manufacturing from calcination of magnesite . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 8
5.2. Manufacturing from other sources . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 8
6. Application of MgO concrete . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 9
7. Conclusions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 10
Acknowledgment . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 10
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 10

1. Introduction the service life of concrete structures. To mitigate the shrinkage cracking
of concrete, many measures have been developed, i.e. including incor-
Cracking occurs when concrete materials undergo restrained volu- poration of fibers into concrete [1], partially replacing Portland cement
metric shrinkage, which has detrimental effects on the mechanical with supplementary cementitious materials such as fly ash, limestone
properties and durability of concrete materials and therefore reduce etc. [2,3], adding shrinkage-reducing chemical agents [4,5], expansive
additives [6,7] or a combination of both [8–10], or providing inner
⁎ Corresponding author. curing (for example using saturated aggregates [11–13], or superab-
E-mail address: andymoliwu@njut.edu.cn (L. Mo). sorbent polymers [14,15]). These measures contribute effectively to

0008-8846/$ – see front matter © 2013 Elsevier Ltd. All rights reserved.
http://dx.doi.org/10.1016/j.cemconres.2013.12.007
2 L. Mo et al. / Cement and Concrete Research 57 (2014) 1–12

mitigating the shrinkage and corresponding cracks in concrete, par- content cement and MEA. Furthermore, ongoing work, as well as forth-
ticularly at relatively early age. coming challenges of MgO expansive cement and concrete, is also in-
Due to the poor thermal conductivity of mass concrete, its tempera- cluded to facilitate international dialog.
ture may increase significantly due to the heat of cement hydration,
which then causes significant thermal shrinkage during the cooling pe- 2. Brief history of MgO expansive cement and concrete
riod which plays an important role in the shrinkage cracking at later
ages. The cooling time needed for mass concrete to reach the normal Attention was first drawn to the expansive behavior of periclase
temperature may last several weeks to months or even years, which in cement in relation to its detrimental effects on the volume stability
depends on the mix proportions, volume of concrete, practice, and envi- of cement materials. In 1884, a number of bridges in France were
ronmental condition. In order to prevent the thermal shrinkage cracking constructed with cement containing 16–30% of periclase which were
in mass concrete, traditional measures such as using cement with low damaged by the delayed excessive expansion of the concrete due to
hydration heat, mixing with high volume of supplementary cementi- the hydration of periclase within it [28]. Meanwhile, the City Hall of
tious materials as cement replacements, pre-cooling the raw materials Kassel, Germany constructed with cement containing up to 27% peri-
and/or post-cooling concrete by embedding cooling pipes are widely clase was destroyed [28]. Since then, significant work has been focused
used to decrease the maximum temperature rise and in turn reduce on the hydration and expansion of periclase as well as the corresponding
the thermal shrinkage [16]. Nevertheless, some of these traditional soundness of the cement. To avoid the unsoundness of cement caused
methods are costly, and sometimes the thermal shrinkage of super by periclase, the content of MgO in cement clinker is limited in the spec-
large mass concrete, i.e. dam concrete, cannot be prevented completely ifications of Portland cement, i.e. 5.0% limit of MgO content for Portland
due to its very long term process. cement in China [29] and the UK [30], and 6.0% in America [31].
Compensation of the thermal shrinkage with delayed expansion of In the 1970s, the Baishan concrete dam in Liaoning province, China
slow hydrating MgO is an effective and economic method of preventing was constructed with a cement containing ~ 5% MgO [17,18], which
the thermal cracking of dam concrete. This approach was first devel- surprisingly developed no cracks in its concrete foundation although
oped in China in the 1970s when Chinese researchers and engineers no temperature control measures were used and over 60% of the foun-
discovered by accident that the thermal shrinkage of mass concrete dation concrete was cast during the summer period with a maximum
in the Baishan Dam was effectively compensated for by the delayed temperature difference of up to 40 °C. Subsequent research revealed
expansion due to the slow hydration of the periclase (MgO) contained that the delayed expansion caused by the hydration of MgO contained
in the cement clinker and thus thermal shrinkage cracking was avoided in the cement clinker effectively compensated the thermal shrinkage
[17,18]. Since then a significant level of laboratory research work and in- within the dam concrete [18]. From then on, Chinese researchers
dustrial practice has been performed in China, and a new technology of and engineers focused on the preparation, hydration, and expansion
rapid dam construction using MgO concrete was then gradually devel- of high MgO-containing expansive cements [32–34], and their compen-
oped [17,19,20]. By using this technology, the costly measures of tem- sation effects on the thermal shrinkage of mass concrete [17]. Subse-
perature rise control for dam concrete were simplified or sometimes quently more dams were constructed in China using MgO-containing
eliminated, which led to significant financial savings and the speeding expansive cements.
up of the construction process [21]. To date, research on MgO expansive In addition to relying on the MgO already present in the cement clin-
cement and concrete in China has covered a very wide range of different ker (calcined at ~1450 °C), whose reactivity is extremely low and thus
aspects, including the preparation, hydration, and expansion properties causes delayed expansion, another approach also used in China dating
of MgO cement (cement containing high MgO content) as well as MgO back to the 1970s has been to prepare the MgO separately by calcining
expansive additive (MEA), performance of MgO concrete, industrial magnesite at predetermined conditions of temperature and residence
manufacturing and application of MEA to name a few. time [17,32,34,35]. Although Mehta [36] in 1980 reported the same
In comparison to the traditional expansive cement or expansive idea, this research was only performed in the laboratory rather than ap-
additives such as sulfoaluminate, aluminate clinker or CaO-based ex- plied in field concrete. Since 1985, the expansive concrete prepared by
pansive additives which are now widely used in Japan, USA and China mixing MEA has been used in concrete dams, and a novel technology
[7,22–25], MgO has many advantages. This includes its chemically of rapid dam construction was developed [17], leading to significant
stable hydration product, namely Mg(OH)2, relatively low water re- technical and economic benefits. These included the reduction or even
quirement for the hydration of MgO, and in particular its designable complete elimination of the costly cooling measures leading to signifi-
expansion properties. Rapid expansion can also be produced by MgO cant financial savings, the speeding up of the construction process as
with high reactivity, which can thus be used for compensating the the concrete could be cast continually with less transverse or longitudi-
shrinkage of concrete at early age. In recent years, the application of nal contraction joints, and the significant reduction of thermal cracks
MEA with high reactivity has been extended to concrete pavement to [21]. To date, over 30 dams have so far been constructed with such
mitigate the drying shrinkage as well as autogenous shrinkage at early MgO concrete in China. As all of these dams have heights less than
age [26,27]. Both the experimental and industrial application experi- 150 m [37], super-large concrete dams with height exceeding 200 m,
ences have shown the benefits of MgO used in compensating concrete which are either currently being or will be constructed in the foresee-
shrinkage and enhancing the durability of concrete. Accordingly, the able future in China, impose new challenges in this area as discussed
dissemination and sharing of this knowledge on MgO-based expansive in this paper.
cement and concrete would be of value to relevant engineers and re-
searchers across the world. However, China is the only country in the 3. Hydration and expansion of MgO in cementitious materials
world that uses MgO cement or MEA in the production of shrinkage-
compensating concrete, and most of the literature related to MgO con- 3.1. Hydration and expansion of dead burnt periclase in cement clinker
crete is published in Chinese and is hence not easily accessible to others.
Moreover, due to the limited rigorous research work and the lack of When in contact with water, the kinetics of MgO dissolution strongly
quality control in production processes of MEA, there is still further depends on the concentration of surface defects of the MgO crystals,
work needed to extend the application of MgO expansive cement and such that the less defects the MgO crystals have, the slower the hydra-
concrete. tion [38]. Under the high temperature of cement clinker production,
This paper presents a review of the development history of MgO ex- ~ 1450 °C, the crystal structure of MgO becomes well developed,
pansive cement and concrete in China, the expansion mechanism and resulting in large grain sizes of MgO and few crystal defects which in
properties, industrial manufacturing and application of both high MgO turn lead to a very slow hydration rate. Kasselouris et al. [39] reported
L. Mo et al. / Cement and Concrete Research 57 (2014) 1–12 3

that the hydration of periclase in cement pastes reached a limited value provide a barrier for the water diffusion to the MgO surface and nor-
of 73.4% at age of 6 years cured in 18 °C water, and thereafter increased mally the surrounding clinker mineral hydrates prior to the hydration
very slightly with increasing ages. According to Lou et al. [40], the of the periclase. Fig. 1(b) shows unhydrated periclase particles still
hydration of periclase is a type of topochemical reaction, of which remains after 1 year of hydration, surrounded by the barrier formed
the reaction rate is controlled by diffusion of reaction ions through the by the anhydrous cement clinker in the cement paste.
hydration product layer of Mg(OH)2. Thus the curing temperature It is well known that the delayed expansion of cement pastes caused
has a significant influence on the hydration of periclase, such that the by MgO is attributed to the formation of Mg(OH)2. Although approxi-
elevated temperature increases the hydration rate of periclase signifi- mately 118% of solid volume increase is caused when MgO transforms
cantly [18,40–42]. The increase of the hydration degree of periclase into Mg(OH)2, the corresponding expansion induced is not precisely
with increasing time and temperature is considered to be according to equal to the increase of solid volume. This may be related to the expan-
Eq. (1) [40,41]: sion mechanism. There are several theories developed to explain
the expansion mechanism of MgO, and two main common theories
2 2=3 are (i) crystal growth pressure due to the growth of Mg(OH)2 and
1− G−ð1−GÞ ¼ K T t ð1Þ
3 (ii) swelling pressure due to water absorption by very small crystals of
Mg(OH)2. Chatterji [43] indicated that during the hydration of MgO, a
where G is the hydration degree, KT is the reaction rate constant, and t is
supersaturated solution of Mg2+ and OH− would firstly form and then
the reaction time.
Mg(OH)2 crystal would precipitate and grow in a confined region,
KT is a function of temperature, which increases with increasing
resulting in crystal growth pressure which leads to the expansion of
temperature T as described in Eq. (2) [40]:
the cement pastes. The crystal growth pressure could be described in
 
4 5446 Eq. (3):
K T ¼ 1:478  10 exp − : ð2Þ
T  
RT a
ΔP ¼  ln s ð3Þ
In addition to the hydration reactivity, the location of periclase Vm a0
formed in cement clinker also plays a role in its slow hydration. As
where ΔP is the crystal growth pressure, Vm is the mole volume of
shown in Fig. 1(a), the periclase typically formed in the cement clinker
Mg(OH)2, as is the mean activity of the supersaturated solution, a0 is
is surrounded by other mineral phases of C3S, C2S, and C3A which
the mean activity of the saturated solution, R is the gas constant, and
T is the absolute temperature. Deng et al. [44,45] found that the pH en-
vironment had a strong influence on the expansion of MgO. In a high pH
environment, more Mg2+ ions were located in a confined region near
the surface of MgO particle due to the limited and short distance diffu-
sion of Mg2+, which thus contributed to a higher supersaturated degree
and thereby resulting in a larger expansion.

3.2. Hydration and expansion of MEA

MEA is typically produced by calcining magnesite at a temperature


ranging from 900 °C to 1200 °C [46–48], which is much lower than
the cement clinker temperature, and as a result has higher hydration re-
activity in comparison to the dead burnt periclase. The calcination con-
ditions have a significant influence on the hydration reactivity of MgO
by affecting the crystal structure of the MgO as well as its specific surface
area [49–51]. The work performed by Mo et al. [49] showed that the
MEA particles consisted of many aggregated micro-grains of MgO with
inner pores, as can be seen in Fig. 2 of a typical SEM morphology of a
MEA particle calcined at 1100 °C for 1 h [52]. During the calcination
under high temperature conditions, the magnesite firstly decomposes

Fig. 1. BSEM images of periclase: (a) Periclase formed in cement clinker and
(b) Unhydrated periclase contained in a cement paste after 1 year curing in water Fig. 2. Typical SEM morphology of MEA particle consisting of aggregated micro-grains
at 30 °C. (P: periclase, A: Alite, B: Belite, Al: Aluminate phase). (calcined under 1100 °C for 1 h) [52].
4 L. Mo et al. / Cement and Concrete Research 57 (2014) 1–12

into MgO nanoparticles, and then the nanoparticles sinter and coarsen
the MgO grain size [53], reducing the crystal defects (i.e. crystal lattice
distortion). Kleiman and Chaim [54] reported that MgO nanoparticles
undergo crystal growth at temperatures as low as 700 °C. With in-
creasing calcination temperature and residence time, the crystal grain
size of MgO increases and the defects of MgO crystal decrease, thus de-
creasing the hydration reactivity of MgO crystals [49,50]. On contact
with water, hydration of MgO occurs at the MEA particle exterior sur-
faces, inner pore surfaces and the crystal grain boundary. Therefore, in
addition to the hydration reactivity of MgO crystals, the specific surface
area plays an important role in the hydration activity of MgO in MEA
as it influences the reaction interface area. The growth of MgO grains re-
duces the total volumes of inner pores and in turn decreases the specific
surface area, thus decreasing the reaction interface and contributing to
the decrease of hydration reactivity [49]. The variables influencing the
hydration and expansion of MgO, and relationship between them are
summarized in Fig. 3.
The hydration reactivity of MgO is typically determined by using Fig. 4. Relationship between the specific surface area and reactivity value of MgO.

weak acid (citric acid or acetic acid) neutralization and defined as


the time required for complete neutralization with the acid solution exceeds that of MEA with high reactivity. The accelerated expansion of
[49,55,56]. This time is usually designated as the reactivity value, and MEA with low reactivity after the induction period is attributed to the
a higher reactivity value implies lower hydration reactivity. As shown fact that the sintered MgO becomes segregated into many smaller
in Fig. 4, with increasing specific surface area, the reactivity value of grains by the expansion at the grain boundary thereby increasing
MgO decreases, indicating an increase in the reactivity of the MgO. the reaction area and in turn accelerating the hydration. The lower the
The figure also implies that the specific surface area influences the reac- activity of the MEA, the longer the induction period is and the larger
tivity of MgO more significantly when it is less than 10 m2/g. However, the “ultimate” expansion at late age.
it should be noted that the decrease in specific surface area is closely re- In addition to the hydration reactivity, the microstructure of MEA
lated to the increase of MgO grain size which also plays an important plays an important role on its expansion behavior [49]. Fig. 6 is an ex-
role in the hydration reactivity (shown in Fig. 3). pansion model of MEA which takes into account the inner pore struc-
The expansion properties of MgO depend on its microstructure and ture of MEA. For MEA with relatively high reactivity, it has a porous
hydration reactivity which are closely related to the calcination condi- microstructure (Fig. 6(a)). The hydration occurs on the exterior surface,
tions (as seen in Fig. 3). When calcined under higher temperature for inner pore surface, and the grain boundary of MgO, and the formation
longer residence time, the MEA produced slower and less expansion of Mg(OH)2 is localized near the MgO due to the short diffusion distance
at relatively early age but more rapid and larger expansion at late age, of Mg2 +, which contributes to the self-expansion of MEA particle. As
and longer time was needed to reach the ultimate expansion [46,49]. the self-expansion of an MEA particle is produced in a confined region
Fig. 5 shows the expansion curves of cement pastes containing 8% originally occupied by the initial MEA particle, the confined expansion
MEA with various hydration reactivities, which was calcined at different produces expansive stress and eventually expands the cement matrix.
temperatures, demonstrating that MEA with high reactivity hydrates Part of the hydration product Mg(OH)2 is filled in the inner pores.
rapidly and thus produces fast expansion at early age, and the expansion The less reactivity the MEA has, less inner pores exist within the parti-
then ceases within short time. In contrast MEA with low reactivity cle as shown in Fig. 6(b), and less accommodation is provided for
hydrates slowly and causes slow expansion at early age, but after an the Mg(OH)2. This implies that less Mg(OH)2 is consumed in filling
induction period, the expansion curve grows rapidly and eventually the inner pores, and thus more Mg(OH)2 would contribute to the

Fig. 3. Variables influencing the hydration and expansion of MgO in cementitious materials.
L. Mo et al. / Cement and Concrete Research 57 (2014) 1–12 5

stress to break the MEA particles into smaller ones which increases
the reaction area dramatically and correspondingly increases the hy-
dration rate as well as the expansion. In conclusion, the expansion
properties of MEA can be adjusted via controlling its microstructures
and hydration reactivity through changing the calcining conditions,
which provides a principle for developing series types of MEA with
various expansion properties.
Expansive stress caused by self-expansion of MEA particles is the es-
sential driving force for the cement paste to expand. However, the ex-
pansion of cement pastes is a result of the competitive effects between
the expansive stress and the resistance response of the cement matrix
(as shown in Fig. 3). Hydrated cement paste is a type of viscoelastic
material, which exhibits both viscous and elastic characteristics when
undergoing deformation, and the viscoelastic property of cement
paste is time-dependent [57,58]. At earlier age, under the same expan-
sive stress, larger viscous deformation of cement paste can be produced
and thus more relaxation, leading to less expansion of the cement paste.
Accordingly, the MEA with higher reactivity hydrates more at early age,
Fig. 5. Expansion of cement pastes containing 8% MEA with various hydration reactivities and hence more expansive stress can be relaxed due to the viscous de-
calcined under different temperatures for 1 h (cured in 40 °C water) [49].
formation of cement pastes, which resulted in smaller ultimate expan-
sion, whereas MEA with lower reactivity produced more expansive
expansion, resulting a larger ultimate expansion. Moreover, the hydra- stress at late age leading to larger ultimate expansion.
tion at the grain boundary of MgO contributes significantly to the ex-
pansion, particularly for the MEA with low reactivity. The expansion 3.3. Factors influencing the hydration and expansion of MgO
produced at the MgO grain boundary may induce enough expansive
The hydration and expansion of MEA are influenced by its particle
size. As the specific surface area increases with the decreasing particle
size of MEA, MEA with smaller particle size has a larger reaction inter-
face with water, leading to greater hydration rate and corresponding
faster and larger expansion at early age. In contrast, the MEA with
coarser particle produces less expansion at early age but larger expan-
sion at late age and larger ultimate expansion as well [59]. Zhang [10]
reported that the lower the reactivity of MEA, the stronger is the influ-
ence of particle size on the expansion. Since MEA with lower reactivity
has smaller inner pore surface area, in comparison to the original inner
pore surface area, the increase in specific surface area of MEA particles
due to the decrease of particle size is more obvious, and thus has
greater influence on its hydration reactivity and the corresponding
expansion. In addition, the coarser particle of MEA may cause larger
self-expansion in a confined region, which thus produces higher
expansive stress. For the same addition percentage of MEA, MEA with
coarser particles can be distributed less homogeneously in the cement
paste and produce a more heterogeneous expansion, which contributes
to a greater expansion as well.
Increasing the added content of MEA in cement increases the expan-
sion of cement pastes. This is understandable that more MgO contained
in cement paste produces more Mg(OH)2, and thus produces larger ex-
pansive stress in the cement pastes, leading to larger expansion. It is
reported that, for the same increase in addition of MEA, MEA with
lower reactivity results in larger increase in the expansion of cement
pastes, implying that for the MEA with lower reactivity, the addition
content has a greater influence on the expansion of cement pastes
[10]. This is probably attributed to the fact that for the less reactive
MEA, more of MgO hydrates at late age, during which less expansive
stress can be relaxed due to the viscous deformation of the cement
matrix, leading to larger expansion.
The curing temperature has a strong influence on the expansion
of MgO as it influences the hydration rate of MgO. At higher curing
temperatures, MgO hydrates faster, and thus produces more rapid and
larger expansion [28]. This is attributed to the MgO hydrating faster
and producing more Mg2+ near the surface of MgO in a short time at
higher temperatures as reported by Chatterji [43], which results in
larger supersaturations and thus increased crystal growth pressure.
Moreover, as shown in Fig. 7, the curing temperature has a more signif-
icant influence on the expansion of less reactive MEA [60]. The relative
Fig. 6. Expansion models of MEA [49] (a) with high reactivity and (b) with low reactivity. humidity of the environment also has an obvious effect on the expansion
6 L. Mo et al. / Cement and Concrete Research 57 (2014) 1–12

the hydration rate of MgO [39]. The slower hydration of MgO may pro-
vide more time for the cement matrix to undergo viscous deformation,
and thus decreases the ultimate expansion. Huang et al. [71] found that
with increasing the addition of MgO or curing temperature, the sup-
pression effects of fly ash on the expansion of MgO decreased.

4. Performance of MgO concrete

4.1. Expansion

The expansion properties of MgO concrete with high MgO content


cement, or with incorporated MEA, have been widely investigated.
Many variables, as shown in Fig. 3, such as reactivity of MgO, added con-
tent of MgO, the curing conditions in terms of temperature and relative
humidity, raw materials and mix proportions of concrete, and the re-
straint conditions influence the expansion process of MgO concrete.
MEA with higher reactivity produces more rapid and larger expansion
in concrete at early age but slower and less expansion at late age [72].
Fig. 8 shows the expansion curves of MgO-containing concrete cured
at 20 °C for 10 years [73]. Accordingly the expansion of concrete
increases with increasing MEA content, and moreover the expansion
process is stable and gradually ceases, and thereafter no obvious volume
changes are observed. Long term investigations on the MgO concrete
samples or in-situ monitoring on dam concretes indicate that the
expansion curve of MgO concrete is stabilized once the hydration of
MgO completed. This is related to the stable chemical properties of
Mg(OH)2, which has very low solubility, being 200 times less than
that of Ca(OH)2.
For the same addition content of MgO, concrete cured at higher
curing temperature exhibits more rapid expansion and reaches larger
ultimate expansion within shorter period [74]. This is related to the
faster hydration of MgO at elevated temperature. Considering the tem-
perature history of field concrete in real construction, the expansion
properties of MgO concrete were widely investigated under different
curing temperatures and/or a various temperature process according
to the simulation of temperature history in the real construction.
Fig. 7. Expansion of cement pastes containing 8% MEA cured in water under different
temperatures [60]: (a) MEA with a reactivity value of 65 s; (b) MEA with a reactivity Water supply for the hydration of MgO is a requisite for MgO concrete
value of 291 s. to produce expansion. Therefore, relative humidity is another factor
influencing the expansion of MgO concrete. Owing to the relatively
low water requirement for the hydration of MgO, under the non-wet
of MgO as water is needed for its hydration. Theoretically 0.45 of water/ condition the autogenous shrinkage of concrete can still be compensated
MgO ratio is needed for the complete hydration of MgO. Cured in water, effectively by MgO [62,64]. However, under drying condition, the expan-
the expansion produced by MgO is more rapid, due to the sufficient sup- sion of MgO is limited due to the lack of water supply [65]. Accordingly,
ply of water, and larger in comparison to being cured under low relative it is beneficial to provide sufficient moist curing conditions for MgO
humidity, non-wet curing condition, or drying condition [61]. Due to concrete in field.
the relatively small water content required for the hydration of MgO,
the MgO is suitable for compensation of autogenous shrinkage under
sealed curing conditions [61–64]. However, under drying conditions,
the MgO could only partially compensate the drying shrinkage due to
the lack of water supply [61,63,65].
Fly ash has mitigating effects on the expansion of MgO [66,67] such
that increasing the addition of fly ash would decrease the expansion of
MgO in cement pastes. There are three main factors that may contribute
to the effect of fly ash. First, the addition of fly ash decreases the pH en-
vironment in cement pastes, which lowers the supersaturation of the
solution and thus reduces the crystal growth pressure of Mg(OH)2,
and in turn decreases the expansion [44]. Secondly, the densification
of cement paste as a result of the pozzolanic reaction, or formation
of high strength products under autoclave condition, improves the
resistance of cement paste to the expansion [68,69]. Thirdly, the addi-
tion of fly ash changes the viscoelastic properties of cement pastes.
According to Ye et al. [70], the pozzolanic reaction of fly ash consumes
the crystal phases of Ca(OH)2, and increases the content of C–S–H,
Fig. 8. Long term deformation of concrete containing MEA. (C-I: Portland cement from
which increases the viscous properties (viscous coefficient) of the ce- Emei, 30% Fa, W/C = 0.60, Cement binder 223 kg/m3; C-II: Portland cement for dam
ment matrix thus reducing the expansive stress, and eventually de- from Dukou, 30% Fa, W/C = 0.52, Cement binder 212 kg/m3; C-III: Portland cement for
creasing the expansion. In addition, the addition of fly ash may reduce dam from Emei, 20% Fa, W/C = 0.6, Cement binder 198 kg/m3) [73].
L. Mo et al. / Cement and Concrete Research 57 (2014) 1–12 7

The expansion of MgO concrete is attributed to the expansion of concrete. Concrete contains less MgO content per unit volume and the
the cement pastes, whereas the large volume of aggregates used in con- aggregates in concrete provide constraints on the expansion of the
crete provides restraints on the expansion of the cement paste. For the cement paste matrix, which contribute to the decrease in expansion
same addition content of MgO, concrete containing larger volume of [86]. As reported, only cement exhibiting an autoclave expansion higher
aggregates has less expansion. Moreover, the exterior constraints also than 15% can produce obvious expansion in concrete under normal
decrease the expansion of concrete [75–77]. curing conditions [28]. The third is that unreasonable evaluation criteria
are used to evaluate the unsoundness. The relationship between the
4.2. Mechanical properties and durability expansion value which is the only assessment index and soundness
has not been well established.
Appropriate expansion of concrete with suitable addition of MgO For MgO concrete, there is no test procedure developed for the as-
may increase the mechanical properties (i.e. compressive strength, sessment of its soundness. Previously the autoclave testing of cement
flexural strength, elastic modulus, tensile strain capacity) [78–80] and was applied to concrete directly. However, the autoclave method is
durability (i.e. increasing freezing-and-thawing resistance and reducing not suitable for MgO concrete, as there is a poor correlation of autoclave
permeability [72]) of concrete. According to Li [78], the expansion of less expansion to the performance of concrete in real field. Fig. 9 shows that
than 500 microstrains (0.05%) may cause no obvious loss in the me- the expansion of MgO concrete specimens under the autoclave test in-
chanical strength of the free concrete. But excessive expansion due to creases with the increasing temperature for the same addition content
high percentage incorporation or unsuitable type of MEA into concrete of MEA. It should be noted that the control concrete specimens without
may result in a decrease in mechanical strength [81]. In fact, the influ- the addition of MEA also expanded. The higher the autoclave tempera-
ence of MEA on the mechanical performance or durability of concrete ture used, the more the expansion of the control concrete. This may be
depends on the influence of expansion produced on the microstructure attributed to the irreversible thermal expansion of aggregates as well
of concrete. The expansion contributes to the optimization of the micro- as the mortar matrix. Thermal stress could be induced at high tempera-
structure of concrete, e.g. decreasing the pore size and total pore ture due to the difference of thermal expansion coefficients of mortar
volumes. It may not only enhance the mechanical strength of concrete, matrix and aggregates. Such thermal stress increases with increasing
but also improve the durability of concrete. However, if expansion temperature and may result in cracking at the interface between the
causes damage to the microstructure of concrete, e.g. inducing cracks, mortar matrix and aggregates. Accordingly, the autoclave test with con-
increasing the pore size and total volume, destroying the interface crete specimens at high temperature is unreasonable. To link the test
microstructures of aggregates and mortars, then the expansion is harm- results of accelerated experiment to the performance of MgO concrete
ful for mechanical strength and durability of concrete. Restraints on in field more reasonably, some measures were taken to make the
the expansion facilitate microstructure densification, particularly the accelerated experimental conditions closer to that of concrete in field,
paste–aggregate interface, of expansive concrete and thus are beneficial e.g. replacing the cement paste specimens with mortars [86], concrete
for the improvement of mechanical strength [82]. Under the restrained specimens [86–89], and even large scale concrete specimens with
conditions, the expansion of MgO causes densification in concrete and the same mix proportions as that used in the field construction
in turn contributes to the increases in mechanical strength [75–77] [86,90,91], lowering the curing temperature from 216 °C to 200 °C
and improvement of the durability of MgO concrete. However, even [87–89,91–93], 150 °C [88,89], or 80 °C [90,94–96]. In comparison to
under restrained condition, if excessive expansion is produced due to dead burnt periclase, MEA has much higher reactivity, which implies
the excessive addition of MgO, the microstructure of concrete can still that lower temperature would be effective enough for accelerating
be destroyed and then decreases the mechanical strength and durability its hydration. It is reported that MEA with reactivity values ranging
[76,77]. Therefore, using a suitable type as well as an appropriate addi- from 78 s to 264 s hydrated completely within 30 days when cured in
tion dosage of MEA to produce the required expansion is vital for 80 °C water, which provides a potential accelerated way to evaluate
avoiding microstructure destruction or mechanical strength loss in the soundness of MgO concrete [94]. In recent years, a large curing sys-
concrete. tem with a diameter of 1.6 m and a length of 6 m was set up to curing
full scale concrete specimens with size of 1.0 × 0.45 × 0.45 m and
4.3. Soundness with the same raw materials and mix proportions used in the real
dams at 80 °C condition at Nanjing University of Technology, China [90].
Delayed expansion of MgO contained in cement clinker may cause
“unsoundness” in terms of causing excessive expansion, deteriorating
the structure, decreasing the mechanical strength of cement pastes
etc. Therefore the soundness of cement needs to be examined prior to
going into the market according to the cement specifications [83,84].
Due to the low hydration reactivity, the hydration of periclase in cement
clinker is extremely slow, and therefore experiments with elevated
temperature are needed to accelerate the hydration of periclase within
a reasonable time. The autoclave test is a typical method used for the
MgO related soundness examination for cement, in which the cement
specimens are cured at high temperature up to 216 °C for several
hours and then the length changes of specimens measured [83–85].
Although the high temperature in autoclave test does accelerate the hy-
dration of MgO significantly, this test is a method far from ideal and may
not reflect the true soundness of cement particularly in concrete be-
cause of three main reasons. The first is that the accelerated conditions
with the high temperature of 216 °C is too critical for the accelerated
hydration of cement as well as MgO. Under such high temperatures,
MgO hydrates rapidly to produce huge expansive stresses, and mean-
while some low strength hydration product C2SH is formed reducing
the resistance to expansion. The second is that poor correlations exist Fig. 9. Effects of temperature on the expansion of concrete in the autoclave test.
between the expansion of cement pastes and the performance of field Data collected from reference [89], autoclave time: 6 h.
8 L. Mo et al. / Cement and Concrete Research 57 (2014) 1–12

For assessing the soundness of MgO concrete, in addition to the residence time and homogeneously heating the magnesite are the key
expansion value, the mechanical strength and even other properties issues for the MEA quality. As large magnesite blocks are usually used
relating to its durability need to be taken into account since the expan- in the shaft and tunnel kilns, the magnesite blocks are heterogeneously
sion may influence the strength and durability of concrete. Fig. 10 heated, thereby resulting in heterogeneous reactivity and expansion
shows the compressive strength ratio of MgO containing concrete to properties. Moreover, for the shaft kiln, there was no automatic moni-
the reference concrete without addition of MgO after the accelerated toring system to adequately control the temperature and residence
curing at high temperature. Accordingly, when the expansion is less time [97]. To obtain a homogeneous calcination condition and produce
than 0.136%, the compressive strength ratio increases with increasing homogeneous MgO, small particle of magnesite are recommend for use
expansion, implying the gentle expansion is beneficial for the compres- in a kiln with precise control of calcination conditions. Several types of
sive strength. However, with continuous increase of expansion, the MEAs with various reactivities were produced at pilot scale by calcining
compressive strength ratio decreases, indicating the expansion has small pieces of magnesite with particle size less than 0.5 cm in a small
induced loss in compressive strength. Therefore, an expansion value of rotary kiln [26], and more recently a large rotary clinker kiln was tried
0.136% could be considered as the threshold value for the expansion to calcine small blocks of magnesite to produce MEA at industrial scale
limit for MgO concrete in this study. For concrete with given raw mate- at Nanjing University of Technology, in China, in collaboration with
rials and similar mix proportion, the threshold value can be obtained industry.
via correlating the mechanical strength change to the expansion. But Product standards are necessary for the quality control of MEA,
for different types of concrete with different materials or various mix nevertheless no such standard has been established for MEA. A prelim-
proportions, the threshold expansion value would be different. inary specification for the light burnt MEA used in hydraulic engineering
was developed in 1994, in which the main control issues for MgO
5. Manufacture of MEA quality were: MgO content ≥ 90%, reactivity value 240 ± 40 s, CaO
content b2%, particle size b3% residue on 0.077 mm sieve, loss on igni-
5.1. Manufacturing from calcination of magnesite tion ≤ 4% and SiO2 b 4% [17]. In terms of the manufacturing process,
the size of the raw magnesite blocks, calcining temperature, and
The decomposition of magnesite into MgO, when calcined at high residence time were recommend to be in the range of 50–150 mm,
temperature, is a typical approach to produce MgO. China has the 1050 ± 50 °C, and 0.5 h respectively [17]. This specification now re-
largest magnesite reserves in the world, and most of which are located quires revision as there are some problem issues which have arisen:
in Liaoning and Shandong provinces. In these regions, shaft or tunnel (1) the temperature used for the reactivity value test via a neutralizing
kilns are widely employed to calcine magnesite, with raw material citric acid solution ranges from 30 to 35 °C, in which such a temperature
sizes ranging from 30 mm to 400 mm, to manufacture MgO. A large variation of 5 °C is too large to achieve a precise and repeatable test
quantity of the MgO is used as the raw material to produce refractory value; (2) there is a lack of quantitative correlation between the neu-
products. In both shaft and tunnel kilns, the calcination of magnesite tralization time and expansion properties and, therefore, it is reasonable
is heterogeneous due to the poor control on the calcination conditions to add the expansion property test as one of the quality control vari-
(i.e. temperature or residence time), and more over a large temperature ables; (3) the particle size range of the raw magnesite blocks from
difference exists in the different areas within the kilns as well as 50 to 150 mm is still too large to allow and ensure a homogeneous cal-
between the exterior and interior parts of large size magnesite blocks. cination in the whole blocks; (4) the neutralization time of a given con-
Rotary and suspension kilns were also used for the manufacturing of centration citric acid solution by MgO is far from ideal for evaluating the
MgO in Liaoning province, although these manufacturing lines were hydration reactivity of MgO particularly for the expansive additive con-
closed due to their higher costs for the manufacturing process in com- taining b90% MgO. The specific surface area could be used as a quality
parison to the shaft and tunnel kilns. control variable as it has a close relationship with the reactivity value,
For the use of MgO as an expansive additive, in addition to the MgO as shown in Fig. 3. Generally, the specifications should cover the chem-
content, the homogeneity of MgO is also an important factor that influ- ical compositions (e.g. the content of MgO, CaO, SiO2, Fe2O3, Al2O3,
ences the reactivity and expansion property of MEA. The reactivity Na2O, and ignition loss), physical properties (e.g. particle fineness, spe-
of MgO is very sensitive to the calcination conditions, particularly cific surface area), and chemical properties (e.g. hydration reactivity,
the calcining temperature. Precisely controlling the temperature and expansion) of various types of MEA. Furthermore, the methods used
for testing the above mentioned properties need to be described clearly
in the specification.

5.2. Manufacturing from other sources

Magnesite is a relatively valuable mineral resource, and hence it is


claimed that magnesite should not be used in the concrete industry
as a low profit added expansive additive. Meanwhile, there are signif-
icant quantities of low-grade magnesites and mineral wastes with
relatively low content of MgO, which could be used to manufacture
MEA. Moreover, such mineral wastes produced during the mining
process are not utilized efficiently and thus cause environmental
problems in the mining region. In addition, some other Mg-bearing
minerals, such as dolomite or serpentine, could also be used as the
raw materials for producing the MEA [98–102]. Potential sustainable
MgO production routes, from seawater and brines, including reject
brines and other Mg-rich wastewaters, particularly when the produc-
tion process involves sequestration of CO2, would be of great signifi-
cance due to the reduced overall carbon emissions [103,104]. Some
production routes are based on the work of Ferrini et al. [105,106]
Fig. 10. The compressive strength ratio of MgO containing concrete to reference concrete. on the production of nesquehonite (MgCO3·3H2O) from magnesium
Data from Cai [89] and Mo [72]. chloride and brines.
L. Mo et al. / Cement and Concrete Research 57 (2014) 1–12 9

6. Application of MgO concrete Generally, expansive concrete is considered to be used in the


constrained region of construction structure. There is some argument
MEA was mainly used in dam concrete to compensate the thermal as to whether the MEA should only be applied in such restrained regions
shrinkage of the mass concrete, resulting in the minimization or of the base foundation concrete or be applied in the whole structure of
complete elimination of the relatively expensive temperature control dam. Additionally, should the concrete in all the structural parts of the
measures in construction. This may account for 4%–6% of the total dam be mixed with the same type and same dosage of MEA? These
investment for a dam, and thus lead to significant financial savings as are very important questions that need to be answered prior to the ap-
well as acceleration of the construction process [19]. In those construc- plication of MgO concrete in super-large dams. In fact, as shown in
tion projects, the MgO concrete was mainly used in the restrained Fig. 11, the shrinkage process (shrinkage time and volume) of concrete
regions of gravity dam, roller concrete, backfill concrete of diversion depends on many variables such as the raw materials, mix proportions,
tunnel, and sometimes for the whole dam concrete [107]. The addition restraint conditions, structure type, environment variables (tempera-
of MgO in dam concrete ranged from 2.0% to 5.5%, which produced ture and relative humidity), and practice. The key element of successful
0.002% to 0.024% of expansions [107]. application is to design well the type of MEA and the mix proportions
Looking ahead, by 2020, the hydropower capacity of China will in- of MgO concrete and precisely control the expansion to match the
crease to 330 million kW [108]. As a result more and more large con- shrinkage of concrete. Thus for dam concrete, the temperature rise,
crete dams will be constructed in China, which provides a potentially thermal stress and the shrinkage of concrete in different structural
huge market for the application of MgO concrete. Currently, several parts of dam need to be predicted firstly via some simulation calcula-
super-large dams higher than 200 m are under construction or being tions following which the optimum expansion process of MgO concrete
planned in the southwest area of China, i.e. on the Jinsha River, Daduhe needed for the complete shrinkage compensating could be predicted.
River, Lancangjiang River etc. Prevention of thermal cracking of these Thereafter, MgO concrete with appropriate mix proportions incorpo-
super large dams is challenging because of their very large volumes rating proper type and percentage of MEA can be designed. Then the
and complicated structures. For the application of MgO concrete in performance of the designed MgO concrete such as expansion, mechan-
these super large concrete dams, some challenges are faced such as ical strength, durability and soundness is tested, providing basic data for
the manufacture of MgO with adequate properties at large industrial the optimization of the concrete design. Some simulation models have
scale, precise control of the expansion process of concrete containing been developed to predict the expansion process of MgO concrete
the appropriate type and addition content of MEA, and evaluation of taking into account the effects of temperature on the expansion of
MgO concrete soundness. The expansion process of MgO concrete MgO [109–112]. Unfortunately, these models are based on some unreal-
needs to be well designed and precisely controlled taking account into istic hypotheses that the ultimate expansion produced at the complete
the effects of temperature, restraint conditions in different structural hydration of MgO is only related to the addition content of MgO in con-
parts, and thermal stress field in dam structure. In addition, the simula- crete regardless of the curing temperature or type of MgO. For a more
tion technology to predict the temperature, thermal deformation, appropriate and reliable simulation of the expansion process of MgO
and expansion process of MgO concrete is important and should be concrete, the influence of curing temperature on the expansion process
improved. Currently, China has launched a national research program and the ultimate expansion should be taken into account [113].
which aims to apply MgO concrete in constructing super-large con- Although the property of delayed expansion caused by MEA has
crete dams. been well known, the potential application of the rapid expansion of

Fig. 11. Design and application of MgO concrete.


10 L. Mo et al. / Cement and Concrete Research 57 (2014) 1–12

high reactive MEA at early age has not been well understood. There is (iv) Soundness is one of the important issues of MgO concrete. For
a significant potential to apply relatively reactive MgO to compensate appropriate evaluation of the soundness of MgO concrete, it
the autogeneous shrinkage of conventional concrete as traditional is important to employ accelerated experimental techniques
ettringite-based expansive additives have been used in civil buildings, with appropriate elevated curing temperature, suitable speci-
underground structures, transportation infrastructures, etc. MEA has al- mens as well as comprehensive evaluation criteria. The closer
ready been used to compensate the autogenous shrinkage of pavement the accelerated experiment conditions are to the environment
concrete in airports [26,114] but there is a significant need for further for field concrete, the more reliable evaluation results can be
research. obtained.
(v) There are some challenges faced for extending the application of
7. Conclusions MgO concrete in super large concrete dam with height N200 m to
prevent thermal shrinkage and in conventional civil engineering
China has almost 40 years' experience in employing MgO to com- as replacement of traditional expansive additive: establishing a
pensate the thermal shrinkage of mass concrete since the effects of specification of MEA as a commercial product, manufacturing
periclase contained in cement on the compensation of concrete shrink- types of MEA with various hydration reactivities and expansion
age was discovered by accident in Baishan dam in the 1970s. This paper properties at large industrial scale with stable quality and
has reviewed the history, performance, industrial manufacturing and extending the resources for MEA manufacture, developing a
application of MgO expansive cement and concrete, the state-of-the- reasonable experimental procedure for soundness evaluation
art progress in the field of MgO concrete in China and the forthcoming of MgO concrete, promoting the simulation technology for
challenges. The main conclusions can be drawn as follows: predicting temperature, thermal stress as well as expansion
process of MgO concrete, and applying MEA in compensating
(i) MgO cement or expansive additive has been mainly used to autogeneous shrinkage and drying shrinkage of concrete at rela-
compensate the thermal shrinkage of mass concrete, particularly tively early age.
in concrete dam with height b150 m, in China. MgO concrete can
be prepared through either mixing with MgO cement or incorpo-
Acknowledgment
rating MgO produced by calcining magnesite as an expansive
additive. Due to the dead burnt nature of periclase in cement
Financial support from The National Key Technology R&D Program
and limitations on its content as a result of soundness issues,
(2011BAE27B01-1), Jiangsu Natural Science Fund (BK2012427), and
MgO cement has limited applications and can only be used for
the research fund of Key Laboratory for Advanced Technology in Envi-
compensation of thermal shrinkage of concrete at late age. In
ronmental Protection of Jiangsu Province (AE201105) are gratefully
contrast, MEA is typically produced separately via calcining mag-
acknowledged.
nesite at 900 °C–1200 °C, of which the hydration reactivity and
expansion properties can be designed through adjusting the cal-
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