Construction and Building Materials 255 (2020) 119381

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Construction and Building Materials

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

Review

Recent progress of magnesium oxychloride cement: Manufacture,

curing, structure and performance
Ke Li a,b, Yuansheng Wang a,b,⇑, Nina Yao c, Aimin Zhang b,⇑
a
College of Naval Architecture and Ocean Engineering, Naval University of Engineering, Wuhan 430033, China
b
State Key Laboratory of Polymers Materials Engineering of China, Polymer Research Institute of Sichuan University, Chengdu 610065, China
c
Sichuan Wanhedongfang Technology Company Limited, Chengdu 610065, China

h i g h l i g h t s

The modified methods were reviewed.

Characterizing MOC cement from micro and macro perspectives.

Water-resistance enhancement acted as key research direction of MOC.

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

Article history: Magnesium oxychloride (MOC) cement has attracted much attention because of its excellent mechanical
Received 19 February 2020 properties, but its poor water resistance has limited the development. Aiming at stimulating the devel-
Received in revised form 20 April 2020 opment of MOC cement, this review examines the detailed modification methods that have been gener-
Accepted 27 April 2020
ated in the relevant fields, with a focus on massive literature. A lot of work in the aspects of matrix
Available online 6 May 2020
performance optimization, various modifiers have been devoted to enhance MOC cement, in which the
research on improving water resistance was highly concerned. Meanwhile, the ways to characterize
Keywords:
the micro and macro performance of MOC cement were introduced, such as strength, softening coeffi-
MOC cement
Performance
cient, microstructure and phase characterization and so on. It is concluded that the compound additives
Water resistance containing phosphate and polymer materials have a good effect on improving the water resistance.
Progress Besides, according to the characteristics of MOC cement, the emphases of future research are prospected.
Ó 2020 Elsevier Ltd. All rights reserved.

Contents

1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2
2. Performance optimization of MOC cement matrix. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2
2.1. Hydration process . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2
2.2. Raw material . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3
2.2.1. Quality of raw material . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3
2.2.2. Ratio of raw materials . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3
2.3. Manufacture and curing process . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3
3. Addition of modifier. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5
3.1. Inorganic additives . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 6
3.2. Organic additives. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 7
3.3. Fiber reinforcement. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 8
4. Performance of MOC cement. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 8
4.1. Micro properties . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 8
4.1.1. Microscopic morphology . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 9
4.1.2. XRD . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 10

⇑ Corresponding authors at: College of Naval Architecture and Ocean Engineering, Naval University of Engineering, Wuhan 430033, China (Y. Wang).
E-mail addresses: [email protected] (Y. Wang), [email protected] (A. Zhang).

https://doi.org/10.1016/j.conbuildmat.2020.119381
0950-0618/Ó 2020 Elsevier Ltd. All rights reserved.
2 K. Li et al. / Construction and Building Materials 255 (2020) 119381

4.1.3. Fourier transform infrared spectroscopy (FTIR) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 10

4.2. Macro performance . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 11
4.2.1. Strength. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 11
4.2.2. Softening coefficient . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 11
4.2.3. Pore distribution . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 11
4.2.4. Thermal conductivity . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 12
4.2.5. Setting time . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 12
5. Future of MOC cement. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 13
6. Conclusions and recommendations. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 13
Declaration of Competing Interest . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 14
Acknowledgments . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 14
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 14

1. Introduction The curing conditions, additional modifier, quality and ratio of

raw materials will have a significant impact on the hydration pro-
Magnesium oxychloride (MOC) cement is a kind of air- cess and products, and controlling the generation of high-
hardening gel material made from light burnt magnesium oxide performance hydrated crystals is conducive to improving product
(MgO), magnesium chloride (MgCl2) and water (H2O), which was performance. In the curing process, temperature and humidity
first discovered by Sorel in 1867 [1–3]. Compared with traditional have obvious effects [20]. If the temperature is too low, the crystal
Portland cement, MOC cement has a series of advantages, such as phases grow slowly. When the temperature is too high, some high-
high strength, fast setting speed, good thermal insulation, and fire temperature phases will be produced and the products are easy to
resistance, so it can be widely used in fields of goods packaging, be warped [21]. It is necessary to keep curing room dry, because
construction materials, thermal insulation materials and biological too much water vapor in the air can make crystal phases hydrolyze,
materials [4–7]. At the same time, MOC cement has low cost, a and the phenomenon of halogenation will appear [22]. Modifiers,
wide source of raw materials, and is energy saving in the produc- including inorganic and organic modifiers, are mainly applied to
tion process [8–10]. The excellent performances of MOC cement improve water-resistance [23–24]. And there are also modifiers
make it an environmentally friendly material with development for reinforcement, such as polymer fiber [25]. High-quality raw
prospects, and relevant studies have attracted a large number of materials help to produce products of high performance, so the
scholars’ attention [11,12]. quality of raw materials is essential. The appropriate ratio of raw
The main phases of MOC cement include MgO, brucite (Mg materials is conducive to the generation of a large number of phase
(OH)2) and crystal phases (phase 3 and phase 5), among which 5, while too much water will lead to the formation of flaky Mg
phase 5 has highest modulus and compactness [13,14], hence the (OH)2, and excess MgO will reduce the workability of cement paste,
strength mainly comes from the contribution of phase 5 [15]. resulting in incomplete hydration [26].
Eqs. (1)–(3) are the theoretical formulas, which describe the reac- However, the defects of MOC cement are obvious. The crystals
tion to generate phase 3, phase 5 and Mg(OH)2 during hydration in the MOC cement are easy to hydrolyze when they meet water,
[15]: forming flaky brucite, which has a high porosity and loose struc-
ture. And loose structure will allow water to contact with internal
3MgO þ MgCl2 þ 11H2 O ! 3MgðOHÞ2  MgCl2 crystals, further promoting crystal hydrolysis, and eventually lead-
 8H2 OðPhase 3Þ ð1Þ ing to serious deterioration of mechanical properties [27]. Addi-
tionally, the raw material ratio of MOC cement and the improper
5MgO þ MgCl2 þ 13H2 O ! 5MgðOHÞ2  MgCl2 production and curing process will result in the performance
degradation, which seriously restricted the development of MOC
 8H2 OðPhase 5Þ ð2Þ
cement [28]. The researches, especially on water resistance, are
facing challenges and it is worthwhile devoting much effort to
MgO þ 2H2 O ! MgðOHÞ2 ð3Þ the research.
In the hydration process, acicular crystals (phase 5) extend to To overcome the shortcomings and study the products with
the space gaps and grow in a staggered manner, interconnect with excellent performance, researchers have done a lot of work on per-
each other and form a dense network structure, which makes the formance improving, and have achieved a lot [29–30]. In this
strength extremely high [16]. The hydration process of MOC review, the performance improvement methods of MOC cement
cement is very complex. In the early stage, Bilinski et al. [17] pro- are introduced, and the modified properties are compared. The
posed the ion reaction theory and Ved et al. [18] presented a point mechanism of modification is analyzed. Moreover, the future
of the mononuclear complex ion polymerization, but these two development of MOC cement is prospected.
viewpoints could not well explain the effects of MgO activity, solu-
tion concentration, temperature and pH on the hydration process.
Afterwards, Yu [3] believed that phases 3 and 5 were directly gen- 2. Performance optimization of MOC cement matrix
erated by Mg2+, OH and Cl. Recent studies have shown [19] that
the main phases are not directly formed by ions, but by mononu- 2.1. Hydration process
clear aquo hydroxoco magnesium complex ions
h i2xy In recent years, it is widely recognized that the hydration pro-
 
Mgx ðOHÞy ðH2 OÞz , OH and Cl . The reaction can be divided cess can be described from the hydration kinetics perspective,
into three stages: neutralization, hydration and crystallization. In and the mechanism varies in different hydration stages [31]. It is
the reaction system, MgO is used to increase the concentration of generally believed that the initial phase is in the gel state and then
Mg2+ and OH in the solution to further promote the hydration crystallizes on the surface of the gel phase. The specific phase for-
process. mation process can be divided into three stages: neutralization,
 K. Li et al. / Construction and Building Materials 255 (2020) 119381 3

hydrolyzing-bridging and crystallization stages. The three stages of hydrates. It will result in the decline of strength, poor water resis-
the hydration process can be illuminated as following equations tance, eventually, the products can’t be put into use.
[19]:
1) Neutralization stage: 2.2.2. Ratio of raw materials
 2þ
H2 O
The raw material ratio of MOC mainly refers to the molar ratio

MgCl2  6H2 O ! MgðH2 OÞ6 þ 2Cl ð4Þ between active MgO, MgCl2 and H2O, which is determined by com-
bining practical production experience and theoretical formula
 2 þ Hþ  þ [41].
MgðH2 OÞ6 ! MgðOHÞðH2 OÞ5 þ Hþ ð5Þ
OH In the 1980s, Urwongse and Sorrell [42] firstly proposed the
 þ ternary phase diagram of MOC cement at room temperature
MgO þ Hþ þ 5H2 O ! MgðOHÞðH2 OÞ5 ð6Þ (Fig. 1), providing important theoretical guidance for the produc-
tion of MOC.
In the neutralization stage, MgO is dissolved in the MgCl2 solu-
As the research continues, people’s understanding of the effect
tion, and neutralized by H+ in the solution, increasing the concen-
of raw material ratio on the performance of MOC cement is more
tration of Mg2+ and OH.
comprehensive [43–45]. The crystal phase composition of MOC
2) Hydrolyzing-bridging stage:
cement is highly dependent on the modulus ratio of MgO/MgCl2/
Hþ
h i2xy
H2O [46,47]. Phase 3 is mainly generated in high concentration
xMg2þ þ ðz þ yÞH2 O ! Mgx ðOHÞy ðH2 OÞz þ yHþ ð7Þ
OH MgCl2 solution, while phase 5 and Mg(OH)2 are generally produced
at a low concentration of MgCl2 [48]. Ye et al. [26] found that when
The increasing concentration of Mg2+ and OH promote the
the molar ratio of H2O/MgCl2 was greater than 15, phase 3 disap-
hydrolyzing-bridging reaction, and the polynuclear aquohydrox-
h i2x - y peared, and the main crystal was phase 5, indicating that adjusting
oco magnesium complex ions Mgx ðOHÞy ðH2 OÞz are produced. concentration of MgCl2 solution and curing temperature could con-
3) Crystallization stage: trol the microstructure and crystal phase of MOC cement (Fig. 2),

thus changing the compressive strength of the product. Zhou
½Mgx ðOHÞy ðH2 OÞz 2xy þ mOH þ ð2p  qÞCl þ kH2 O et al. [49] predicted the phase composition of MOC cement through
 the thermodynamic model, and they believed that when MgO/
! ðx  pÞMg2þ þ ½Mgp ðOHÞq ðH2 OÞr 2pq ð2p  qÞCl  ðk þ z
MgCl2 (molar ratio) was between 11 and 17, MOC cement had
 rÞH2 O þ ðy þ m  qÞOH ð8Þ excellent strength and abrasive resistance due to the abundance
where, x, y, z, m, k, p, q, r are the parameters of Eqs. (7) and (8). If of phase 5.
p = 6, q = 10, and k + z-r = 8, In practice, there is no clear guideline on what is the appropri-
 ate ratio of raw materials for MOC cement. It is generally believed
½Mgp ðOHÞq ðH2 OÞr 2pq ð2p  qÞCl  ðk þ z  rÞH2 O can be expressed
 2þ that the ultimate goal is to make the phase 5 content the highest.

as Mg6 ðOHÞ10 2Cl  8H2 O, another expression of In the production process, MgO cann’t fully participate in the reac-
5MgðOHÞ2  MgCl2  8H2 O(phase 5). tion, so the molar ratio of MgO/MgCl2 should be slightly higher
h i2xy than 5. Generally, when MgO/MgCl2 = 7–9, the obtained strength
Mgx ðOHÞy ðH2 OÞz , Cl and H2O attract each other, forming
of products is predominant. In other word, the concentration of
cross-linked amorphous gels, which are eventually converted into MgCl2 determines the formed crystal phase, and 28.9% is the theo-
crystals. With the passage of hardening time, the voids in the net- retical concentration of MgCl2 solution when all hydrates are phase
work structure are gradually filled with crystallization products, 5. When the concentration is higher than this value, phase 3 will be
and the performance of MOC cement is continuously improved. generated. If the concentration is lower than 28.9%, Mg(OH)2 is
formed. On the other hand, the higher the concentration of MgCl2
2.2. Raw material solution, the thicker the cement slurry, the worse the workability
and the less complete the hydration, which may lead to the reduc-
2.2.1. Quality of raw material tion of strength, halogenation and other adverse effects. Consider-
The basic raw materials of MOC cement are composed of lightly ing the mixture workability and comprehensive properties of MOC
burned magnesium oxide, MgCl2 and H2O. It must be particularly cement, the concentration of MgCl2 should be slightly lower than
noted that there are strict requirements for the active content of 28.9%, at which point the hydration products are phase 5 mainly
MgO [32–34]. The quality of MgO largely determines the perfor- and supplemented by Mg(OH)2.
mance of MOC cement products, for example, the calcination tem-
perature, particle size, and activity of MgO have a fatal influence on 2.3. Manufacture and curing process
MOC cement [35,36]. The content of impurities in raw materials
must be strictly controlled [37]. Chlorides of alkali metals have The crystal phase composition, microstructure, mechanical
strong moisture absorption and do not participate in the hydration properties and hydration process of MOC cement are closely
reaction. They exist in a free state, and the higher the content of related to the production process [25,49–51]. He et al. [19] found
chlorides, the more easily the product absorbs moisture [38,39]. that increasing the stirring speed could significantly change the
SO2
4 ion is easy to react with MgO to produce MgSO4, which seri- surface viscosity of MOC cement, and the mechanical properties
ously make the strength and water resistance deteriorate. There- of products stirred at the speed of 280 rmp for 25 min reached
fore, the content of SO24 ion should be reduced as far as possible. the optimum (Fig. 3). Short mixing time and mixing unevenly are
Literature [40] pointed out that the activity of light burnt MgO easy to lead the production of bubbles, which will make mechani-
could not be too low or too high, and the qualified MgO should cal properties degrade. Moreover, excessive mixing will result in
meet the following requirements: activity of about 60%, fineness the deterioration of workability. Controlling the speed and time
less than 200 mesh, free content of CaO < 2%, content of of stirring properly can make the MgCl2 solution and MgO powder
Fe2O3 < 1.5%, and content of SO4 2 in MgCl2 < 3%. fully mixed, reduce the presence of free water, avoid the formation
The disqualification of raw materials will not only cause the of holes and improve the microstructure, therefore, strengthen the
uneasiness, heat concentration of hydration, warping and cracking mechanical properties. Abdel-Gawwad and Khalil [52] used an
of products in the early stage, but also affect the formation of innovative one-part MOC cement manufacture method, which
4 K. Li et al. / Construction and Building Materials 255 (2020) 119381

Fig. 1. Ternary phase diagram at 23 ± 3℃ of MOC cement [42].

Fig. 3. Compressive strength of MOC cement stirred at 140 and 280 rpm [19].
Fig. 2. The relation schema of phase 5, temperature, and water ratio (the color
means the percentage of phase 5) [26].

or isolated air [54]. When H2O/MgCl2 is around 13 at low temper-

was realized by control in the neutralizing, hydrolyzing-bridging ature or room temperature (8–25 °C), the content of phase 5 is very
and condensation rates of MOC-formation. When MgO/MgCl2 high and phase 3 almost does not exist [26]. When the concentra-
molar ratio was 14 and H2O/MgO ratio was 0.1, the performance tion of MgCl2 solution is slightly higher, phase 3 will be formed.
of MOC cement was the best. Both phase 3 and phase 5 are metastable crystals, and phase 3 is
After the MOC cement sample is demolded, it comes to the cur- more stable than phase 5 [48]. However, if the temperature is
ing stage, and the crystal phases (phases 3 and 5 mainly) will be too high, some by-products like brucite will be produced, which
formed [53]. The crystal phases are hydrates, and they are extre- will make the performance worse. High temperature will help
mely sensitive to the ambient temperature and humidity. The cur- the reaction with high activation energy, and the activation energy
ing temperature and humidity have an important influence on the required for the formation of brucite is greater than phase 5, so the
formation of the crystal phases and the microstructure of cement higher the temperature, the more favorable it is for the formation
products [20], and the product usually requires curing in dry air of brucite [55]. When the temperature rises above 72 °C, phase 5
 K. Li et al. / Construction and Building Materials 255 (2020) 119381 5

Fig. 4. Crystal structures of the phases: (a) phase 3; (b) phase 5; (c) chlorocarbonate (note that the hydrogen positions are not defined in panels a and c) [8].

will lose 2 mol of water [8]. If the temperature is greater than 80 °C, nated by the above methods. Phases 5 and 3 will decompose in a
the structure of phase 3 will be damaged [29,56–57]. Due to a large high humidity environment, which can be described by Eqs. (9)
amount of heat released during the hydration process, MOC and (10) [22]:
cement can reach high temperature without heating, making 
scholars curious about the crystal phase at high temperatures. 5MgðOHÞ2  MgCl2  8H2 O ! 5MgðOHÞ2 þ Mg2þ þ 2Cl
After studying the components of MOC cement at 50–150 °C, þ 8H2 O ð9Þ
Bianco [58] proposed the concepts of 2-1-2 phase and 3-1-1 phase.
Dinnebier et al. [21] pointed out that 9-1-4, 2-1-4 and 2-1-2 phases 
3MgðOHÞ2  MgCl2  8H2 O ! 3MgðOHÞ2 þ Mg2þ þ 2Cl
would be produced at 120℃, and they were all unstable at room
temperature. In the hydration process, 9-1-4 phase rapidly chan- þ 8H2 O ð10Þ
ged into a relatively stable phase 3, and this conclusion was veri-
As shown in the above equations, the decomposition of phases 5
fied in literature [59]. A brief description of the hydrated phases
and 3 results in the generation of loosely structured brucite. Com-
at different temperatures is shown in Table 1.
pared with phases 5 and 3, brucite has very poor performance, so
Because of the excellent mechanical properties, phase 5 is con-
the performance of MOC cement is seriously deteriorated. Zhang
sidered to be the best crystal phase in MOC cement. To produce
and Deng [63] pointed out that the phases 3 and 5 are strong acid
MOC cement of superior quality means that the content of phase
and weak base salts. In the water environment, they will hydrolyze
5 needs to be as high as possible. According to literature [54], if
to form a small amount of hydrochloric acid, which will dissolve
curing temperature is low (25℃) in the early stage and high
part of brucite and produce soluble magnesium chloride, thus fur-
(70℃) in the middle and late stages, the growth of phase 5 will
ther damaging the composition and structure of MOC cement and
be facilitated, thus, the MOC cement product will possess out-
greatly reducing its performance. Moreover, when the MOC
standing mechanical properties.
cement is immersed in hot water, the product’s performance
degrades more rapidly and severely [29].
3. Addition of modifier Improving the water-resistance of MOC cement remains an
ongoing challenge in this field, and the most common method is
Using qualified raw materials and adopting reasonable produc- the use of additives for compound modification [64]. The water-
tion and curing processes can effectively guarantee the MOC resistance modifiers mainly include inorganic additives and
cement products have good mechanical properties. However, poor organic additives. If the mechanical properties need to be
water resistance, the fatal defect of MOC cement, can’t be elimi- enhanced, reinforcing fiber is a kind of ideal modifier. When choos-
6 K. Li et al. / Construction and Building Materials 255 (2020) 119381

Table 1 3.1. Inorganic additives

hydrated phases of MOC cement.

Phase Composition Formed Structure Inorganic additives are usually compounded with MOC cement
temperature in the form of microadditive to improve water-resistance, and the
3-1-8 (phase 3) 3Mg Around 10– Cl and H2O ones with obvious effects are phosphoric acid (or phosphate) and
(OH)2MgCl28H2O 55℃ [26] intercalated mineral admixtures.
between two Mg Phosphoric acid and soluble phosphate have relatively good
(OH)4(OH2)2
octahedra chains
modification effects on improving the water-resistance of MOC
[62]. Fig. 4(a) cement [65], which was first proposed by Stewart in 1932 [66].
5-1-8 (phase 5) 5Mg Around 10– Triple chains Subsequently, the modification by phosphoric acid and phosphate
(OH)2MgCl28H2O 30 °C [48– composed of two Mg gradually gained a lot of attention. Deng [22] studied the effect of a
49] (OH)4(OH2)2and one
small dosage of soluble phosphate on MOC cement, and found that
Mg(OH)6 octahedra,
with disordered Cl the strength retention rate with 0.74 wt% H3PO4 reached 96%,
and H2O intercalated while that without H3PO4 was only 6.4%. Chen [23] observed the
[62]. Fig. 4(b) effect of phosphoric acid on the crystal phase through Scanning
2-1-2 2Mg Above 100 °C Infinite triple chains Electron Microscopy (SEM), and the microstructure image showed
(OH)2MgCl22H2O [60] of edge-linked
that adding 1 wt% phosphoric acid made the thick columnar crystal
distorted MgO6
octahedra [55]. thin and round, and the edges and corners of phase 5 were blurred.
2-1-4 2Mg Above 100 °C Parallel structures Zhou et al. [49] figured out that the addition of NaH2PO4 changed
(OH)2MgCl24H2O [21,60] separated by the phase boundary of MOC cement (Fig. 5), and verified that phos-
interstitial one
phate ions had affected the formation conditions of the phases. Li
dimensional zigzag
chains of disordered et al. [67] found that gel-like phase 5 was generated in the MOC
Cl and H2O [60]. cement with KH2PO4, and the higher the content of gel-like phase
9-1-4 9Mg Above 100 °C Infinite triple chains 5 was, the better the water-resistance was. Zhang et al. [68] added
(OH)2MgCl24H2O [21,61] of the MgO6 phosphoric acid and 5-phase seed crystal to MOC cement at the
octahedra linked by
same time, achieving the goal of simultaneously improving
double chains of the
MgO6 octahedra strength and water-resistance.
[21]. Phosphoric acid can improve the water-resistance of MOC
Chlorocarbonate Mg2(OH) Room A 15-membered cement, mainly because of the existence of phosphate ions. It is
ClCO32H2O temperature puckered ring
claimed that insoluble phosphate is formed, which protects the
[62] around Mg
octahedral [62].
phase 5 from hydrolysis [61]. Adding phosphoric acid into MgCl2,
Fig. 4(c) the ionization of phosphoric acid would occur [69]:

H3 PO4 () H2 PO4 þ H þ
ð11Þ

H2 PO4 () HPO2
4 þH
þ
ð12Þ

þ
HPO2 3
4 () PO4 þ H ð13Þ

HPO2 4 tends to be combined with the Mg

2+
in the solution, and
a kind of stable phase with high water-resistance, i.e.
MgPO4  3H2 O, will be produced [70]. Meanwhile, MgPO4  3H2 O
can change the contact points to reinforce the conglutinated force
of the phases, so the compactness enhanced is and the water-
resistance of MOC cement is improved [71]. The mechanism of sol-
uble phosphate to improve the water-resistance of MOC cement is
similar to that of phosphoric acid.
Nevertheless, Deng [22] didn’t find insoluble phosphate in X-
ray Diffraction (XRD) test, and explained that phosphate ions could
reduce the concentration of Mg2+ in the solution, making the main
crystal phases (phases 3 and 5) more stable in water. Thus, the
modified mechanism of phosphate needs to be further studied.
Besides the inorganic acid, some organic acids such as citric acid
[72] and tartaric acid [73,74] also showed the improvement influ-
ence on the water-resistance.
Mineral admixtures mainly refer to a kind of material contain-
ing active SiO2, such as fly ash, silica glass power and so on [75–
77]. The active SiO2 refers to the SiO2 with high specific surface
Fig. 5. The equilibrium phase diagram of MgO-MgCl2-H2O with 0.5 wt% NaH2PO4 at
area, which can react with MgO to form insoluble silicates, i.e.
25 °C (the dotted line is the phase diagram without phosphate) [49]. 3MgO  4SiO2  H2 O and MgSiO3 [70]. And the relevant reactions
are illustrated in Eqs. (14) and (15). The content of SiO2 that can
participate in the reaction is called the active proportion. The reac-
tion is able to consume the excess Mg2+, and the insoluble silicates
ing the additives, according to the performance requirements, the can reduce the concentration of soluble Mg2+, block the pores
influence of factors such as doping amount, particle size and pH between the crystals, to reduce the porosity and improve the com-
on the product must be taken into consideration. pactness of the cement [78–81].
 K. Li et al. / Construction and Building Materials 255 (2020) 119381 7

Fig. 6. Hydration schematic diagram of MOC cement [84].

3MgO þ 4SiO2 ðactiveÞ þ H2 O ! 3MgO  4SiO2  H2 O ð14Þ water-soluble or water-emulsion polymers, which can be blended
evenly with the MOC cement matrix and avoid agglomeration. This
-
Mg2þ þ SiO2 ðactiveÞ þ 2OH ! MgSiO3 þ H2 O ð15Þ kind of modifier will not affect the hydration process of MOC
cement. It is usually coated on the outer wall of crystal phases to
It is reported that the strength retention rate with 30 wt% fly ash
prevent the combination of water and Cl ions. Moreover, it also
was 80% after 28 days’ soaking, and compared with the samples
fills the capillary channel inside the material to prevent the immer-
without fly ash, the water-resistance had been greatly improved
sion of water and reduce the occurrence of scumming [90]. Li et al.
[82]. Mixing fly ash to MOC cement will increase the number of
[91,92] figured out that EVA emulsion has good compatibility with
amorphous phases in the curing process [83], such as magnesium-
MOC cement, which could strengthen the interface between crys-
chloride-silicate-hydrate gel (M-Cl-S-H gel) and magnesium-
tal and glass fiber, so as to improve stress resistance and cracking
chloride-hydrate gel (M-Cl-H gel). The addition of fly ash helps sta-
performance.
bilize the crystal phases, making the acicular phase 5 appear as floc-
The modification ability of a single modifier is limited, and it is
culation. Fig. 6 shows the hydration schematic diagram of MOC
easy to bring the degradation of other properties. The compound
cement with different content of fly ash, implying that with the
of a variety of modifiers may have a surprising influence on MOC
increase of fly ash content, the flocculation volume becomes smaller
cement. Xu et al. [88] fabricated a composite water repellent by mix-
[84]. Silica glass power (SGP), as a modifier, can slow the setting time
ing styrene/acrylic emulsion with inorganic additives such as cal-
and enhanced water-resistance, but the strength of MOC cement
cium superphosphate, and the composite additives made the
decreases slightly [85]. Because of the formation of forsterite, the
softening coefficient increase to 0.97. Furthermore, the MOC cement
pores in the cement will be filled, inhibiting the decomposition of
bricks with this modifier were not scumming, not warping and not
phase 5 and preventing the formation of brucite [85]. Adding incin-
contracting for 360 days at room temperature. Li et al. [10] created
erated sewage sludge ash (ISSA) to MOC cement will generate insol-
a compound modifier with stearic acid–styrene acrylic acids and
uble M-Cl-S-A-H gel, and it can protect the phases 3 and 5 from
phosphate, which can effectively reduce the water absorption and
hydrolysis [86]. Aiming to further improve the water-resistance, a
overcome the buckling deformation. The presence of phosphate ions
small amount of calcium element can also be added to slag, so that
helped to overcome the problem of poor water-resistance. In addi-
the strength can be effectively maintained [87].
tion, the hydrophobic groups of the copolymer emulsion could par-
Researches indicates that inorganic materials such as FeSO4 [65]
tially permeate into the pores and capillaries of MOC cement, and
and rice husk ashes (RHAs) [88] also play a certain role in the
the groups were orientated on the surface of crystal phases. In this
water-resistance enhancement of MOC cement. The addition of
way, the structure becomed more compact, and the surface charac-
inorganic fillers tends to decrease some properties of MOC cement,
teristics of pores were improved.
such as the retarding effect of phosphoric acid [71], which reduces
There are two main purposes for the modifier: One is to
the micro-compactness of MOC and leads to the damage of
enhance the compressive or flexural properties of MOC cement,
strength. Besides, it is necessary to pay attention to the amount
and the other is to improve the water-resistance (softening coeffi-
of the filler. Excessive additives will make the sample retarding,
cient), which is also the focus of research. Whether by blocking the
cracking and present other defects.
micropores or forming a water-resistant gel phase, the purpose is
3.2. Organic additives to prevent the crystal phases from contacting with water, avoiding
the hydrolysis of crystal phases. Besides the use of additives, the
In general, polymer materials have good hydrophobicity. As the goal of hydrophobicity can also be achieved through structural
organic additive, polymer materials can be combined with MOC design. Gao et al. [93] prepared MOC cement with the superhy-
cement to effectively improve the water-resistance of MOC cement drophobic surface by nano-casting technology, and the superhy-
products [24,89]. Organic water-resistant modifiers are usually drophobic surface possessed the function of self-cleaning (Fig. 7).
8 K. Li et al. / Construction and Building Materials 255 (2020) 119381

Fig. 7. MOC cement with the superhydrophobic surface [93].

3.3. Fiber reinforcement using plant fiber to modify MOC cement, necessary interface treat-
ment should be carried out to enhance the interface bonding
Cement is a kind of brittle material, to reinforce the toughness performance.
of cement, fibers are often used in the engineering application. When fiber is bonded well with the MOC cement matrix, the
There are a large number of chlorine ions in MOC cement, which stress is transferred from the matrix to the fiber, improving the
have a strong corrosive effect on metals [94,95]. Therefore, it is toughness. At the same time, the combination of fiber and cemen-
hard for steel to be used as the MOC cement enhancement [96– titious material can eliminate the appearance of cracking. How-
98]. Whereas, glass fiber, polymer fiber and plant fiber are capable ever, when the fiber content is too large, the phenomenon of
of the reinforcement [25,99]. The flexural strength of MOC cement agglomeration is may occur, or the fiber can’t be fully wrapped
reinforced by glass fiber could reach 91.7 MPa, and it had a certain and bonded by MOC cement paste. And it may even cause internal
water-resistance due to the addition of water resistant modifier cavitation, resulting in the decline of the strength of the cement.
[100]. Zhou et al. [6] used polyvinyl acetate (PVA) and glass fibers
to reinforce wood-MOC composites. The fibers were oriented in the
cement matrix by extrusion molding, which effectively improved 4. Performance of MOC cement
the mechanical properties of the composites. He et al. [101] added
waste wood fiber into MOC cement to produce wood-plastic com- Through various modifications, the hydration process, mechan-
posite materials with good flexural capacity, heat preservation and ical properties and crystal morphology of the MOC cement were
noise reduction. The composite materials have the advantage of affected, and the properties of the material were improved. To
environmental friendliness, and the materials can be used as heat explore the mechanism of modification, the researchers have car-
preservation and sound insulation materials. Wang et al. [102] ried out a comprehensive characterization of the micro and macro
made straw/MOC light-weight materials, but found that there properties of MOC cement, looking forward to manufacturing
were interface problems between fiber and MOC cement. Due to products with better performance.
the existence of the smooth waxy layer on the surface of straw,
there were weak interface layers between straw and matrix, which 4.1. Micro properties
was difficult to closely bond. When the micro-cracks were gener-
ated and extended to the periphery of straw, the straw was com- Besides the phase composition of materials, the microstructure
pletely pulled out of the section, which did not give full play to of MOC cement is one of the crucial factors affecting the macro-
the crack resistance effect of plant fiber (Fig. 8). Therefore, when scopic properties [103]. The macroscopic properties such as

Fig. 8. Fracture process of straw/MOC composite [102].

 K. Li et al. / Construction and Building Materials 255 (2020) 119381 9

strength and porosity are the macroscopic expression of the micro- interconnect with each other and form flake crystals in a compact
scopic characteristics of materials. Exploring the microstructure is position, while only the phases in the voids present needle shape.
beneficial to reveal the mechanism of MOC cement composites. Chau and Li [106] observed the microscopic morphology of MOC
cement crystal with different ratios of raw materials, and they
illustrated that there were small particles on the surface of acicular
4.1.1. Microscopic morphology
crystals. When the content of MgO was low, the crystal phase pre-
In the study of MOC cement, Scanning Electron Microscopy
sented an irregular shape. When MgO/MgCl2/H2O was 6.8/1/10
(SEM) is mainly used to observe the morphological characteristics
(molar ratio), the mechanical properties were the best, and the
of the crystal phase. Tooper and Cartz [104] discovered that the
microscopic crystal morphology was more uniform and compact.
shape of phase 5 was rod-like through SEM images, claiming that
Phosphoric acid is considered to be a kind of promising inorganic
the cross part of acicular crystal was enhanced (Fig. 9). Later, Mat-
water resistant modifier. Obviously, the needle-like phase crystals
kovic et al. [105] confirmed that the crystal phase of MOC cement
can be found on the surface of MOC cement with phosphoric acid,
presented acicular shape through SEM. In fact, the phases usually
while the surface morphology without phosphoric acid is amor-
phous or gel-like [71] (Fig. 10).
Meanwhile, the EDX test is often applied as supporting analysis
of SEM to quantitatively detect the element content of crystals
[106]. Hu et al. [107] used EDX to analyze the element content of
phase 5, and the results implied that the test values were highly
consistent with the theoretical values (Table 2). EDX analysis will
detect gold element from the coating material, which should be
ignored. Only the signals of magnesium, oxygen and chlorine ele-
ments are devoted to calculating the atomic percentage, while

Table 2
EDX analysis result of phase 5 [107].

Crystal Element Atomic percentage/%

Theoretical Experimental
Average Standard deviation
Phase 5 O 69.2 70.4 3.2
Mg 23.1 22.5 1.9
Cl 7.7 7.2 1.6
Fig. 9. Two needle-crystals of MOC cement [106].

Fig. 10. Surface morphology of MOC cement: (a and b): without H3PO4; (c and d): with 0.5 M H3PO4 [71].
10 K. Li et al. / Construction and Building Materials 255 (2020) 119381

Fig. 11. XRD patterns of MOC cement specimen before and after 28 d of water soaking (a) Sample A1, (b) Sample A2, (c) Sample A3, (d) Sample A4 [68].

Table 3 quantitative analysis [84], to further probe the crystal characteris-

Mixture design of the MOC cement pastes [68]. tics of MOC cement and the content of each phase at different
Sample A1 A2 A3 A4 stages.
Mass fraction of 5-phase seed crystal/% 0 1 0 1
Mass fraction of H3PO4/% 0 0 1 1
4.1.3. Fourier transform infrared spectroscopy (FTIR)
FTIR is capable of detecting the chemical structure of crystal
phases in MOC cement, which can be used as one of the criteria
for the success of modification. Tan et al. [60] did not find the
hydrogen cannot be detected by EDX because the device is not sen-
vibration peak of H3PO4 in the phosphoric acid modified MOC
sitive to hydrogen atoms.
cement, but discovered the presence of P-OH and PO3 4 , indicating
that phosphoric acid was completely integrated into the cement
4.1.2. XRD matrix. Fig. 13 supports the FTIR spectra comparison of composites
XRD analysis is based on the different characteristics of X-ray in modified with tartaric acid (TA-MOC), phosphoric acid (PA-MOC),
different crystals to identify the phase composition of MOC and in the picture MOC cement with non-additive is expressed as
cement. It can be seen from Fig. 11 (The mixture design is exhib- N-MOC [73]. The absorption bands at 3610.3 cm1 and
ited in Table 3) [68], when MgO/MgCl2/H2O = 6.5/1/13 (molar 3698.2 cm1 are mainly generated by OH stretching vibrations
ratio), MOC cement was mainly composed of phase 5 and a small in phase 5 and Mg(OH)2. After adding tartaric acid and phosphoric
amount of unreacted MgO, while the presence of phase 3 was acid, the peak ratio of 3610.3 cm1 to 3698.2 cm1 increased sig-
not detected. The water-resistance of MOC cement with phospho- nificantly, hinting that the contents of phase 5 in TA-MOC and
ric acid is remarkable, and the phase composition after soaking is PA-MOC were higher than that of N-MOC. Meanwhile, the absorp-
almost unchanged (Fig. 11(c) and (d)), while the phase 5 of the tion bands of 3000–3600 cm1 were produced by oxhydryl bond
sample without phosphoric acid are almost all hydrolyzed to Mg stretching vibration, and the bands between 1600 and 1640 cm1
(OH)2 (Fig. 11(a) and (b)). Owing to the existence of free H+ in were attributed to H-O-H bending.
the early stage of hydration, the characteristic peak of 2-1-2 phase The characterization of MOC cement performance needs to be
was detected for hydration of 30 min [72] (Fig. 12), and 2-1-2 analyzed from macro, micro and multiple perspectives to fully
phase gradually transformed into phase 5 with the increase of prove the reasons for the improvement of material performance.
time, which was consistent with the views in literature [55,71]. For a more comprehensive characterization, researchers are con-
In addition to analyzing phase composition, XRD can also be stantly innovating research methods with high efficiency and good
applied for approximate measurement of phase size [106] and reliability. For example, Dorrepaal and Gowen [7] created a way to

Fig. 12. XRD patterns of MOC cement for various times [72]. Fig. 13. FTIR spectra of MOC cement [73].
 K. Li et al. / Construction and Building Materials 255 (2020) 119381 11

Fig. 14. The compressive strength and flexural strength of MOC cement products [5,10,30,41,54,81,101,108,109,110].

study the heterogeneity of MOC cement by combining Raman will increase [10,101], whereas, the compressive strength will
chemical mapping and NIR hyperspectral chemical imaging. not be affected significantly.
In particular, it should be noted out that when additives are
used for modification, an appropriate amount of additives is bene-
ficial to the strength, but excessive additives will cause a sharp
4.2. Macro performance decline of the strength [108]. Moreover, because stress has an obvi-
ous rate response characteristic, the loading mode will affect the
4.2.1. Strength test results. The existing studies have investigated the strength
Strength is an index to measure the resistance to external loads with different loading rates [26,71,84], and the results can’t be
of MOC cement. For building structure materials, compressive compared directly, so the research should be carried out with the
strength and flexural strength are particularly essential, which rep- results under the same loading mode. Furthermore, MOC cement
resent the structural support capability and bending resistance has the characteristic of quick hardening, and the growth of
capacity respectively. strength becomes slow as time passes. The strength of the first
The compressive strength of MOC cement is significantly 7 days reaches about 90% of the strength in 28 days [54]. After
affected by the ratio of raw materials, curing condition and the 28 days, the strength becomes relatively stable.
addition of modifiers. Fig. 14 shows the compressive and flexural
strength of MOC cement products, which are modified by different 4.2.2. Softening coefficient
methods. It can be seen that the strength of MOC cement will be The softening coefficient, also known as water-resistance coef-
greatly improved if appropriate modification means are adopted. ficient, represents the resistance to water erosion of MOC cement,
For example, through reasonable adjustment of curing conditions, and it is characterized by the compressive strength retention rate.
the compressive strength of MOC cement could reach about The smaller the strength loses after soaking, the higher the soften-
150 MPa [54]. While the MOC cement cured at 75 °C would only ing coefficient will be. The softening coefficient can be defined as
get a compressive strength of around 70 MPa. MOC cement foamed the following equation:
material has good thermal insulation performance, but the com-
pressive and flexural strengths are much lower than those of Rf ¼ Rx =Ro ð16Þ
MOC cement, owing to the porous structure [5]. The combination where, Rf is the softening coefficient, Rx is the compressive strength
of fiber will enhance the toughness, that is, the flexural strength after soaking, and Ro is the compressive strength before soaking.
The softening coefficient of MOC cement modified in different ways
is shown in the Fig. 15. It can be seen from the figure that the water-
resistance of MOC cement is extremely poor, and the strength
decreases significantly after soaking. Through water-resistant mod-
ification, the water-resistant ability of MOC cement can be effec-
tively improved. At present, the most efficient way is the
compound modifier mixed with phosphate and polymer materials
[69]. Poor water-resistance is the most important factor restricting
the development of MOC cement, so the researchers must focus
more on the improvement of the softening coefficient, while the
strength can’t be reduced.

4.2.3. Pore distribution

The porosity of MOC cement refers to the ratio of the volume
occupied by internal voids to the volume of MOC cement in the
natural state, and the porosity is closely related to density, strength
and thermal conductivity. Mercury injection (MIP) [73] is usually
used to investigate the porosity, and it also can be calculated by
density [71]. Different test methods may result in some differ-
Fig. 15. Softening coefficient of MOC cement modified in various ways ences. The relationship between density and contents of form-
[27,30,54,68,73,108]. stable phase change material (FSPCM) is shown in the Fig. 16(a)
12 K. Li et al. / Construction and Building Materials 255 (2020) 119381

Fig. 16. Performance of MOC cement-based composites: (a and b) density and pore volume distribution of MOC/FSPCM composites; (c and d) cumulative intruded pore
volume and different intruded volume vs pore diameter of MOC cement with inorganic acid (N-MOC, TA-MOC and PA-MOC refer to MOC cement with no modifier, tartaric
acid and phosphoric acid respectively) [73,110].

[110]. It can be seen that the high content brought low density of introduction of bubbles in the material can greatly reduce its ther-
MOC/FSPCM composites, and the addition of FSPCM made mal conductivity, for example, mixing cenospheres into MOC
microstructure loose, thus the corresponding strength was poor. cement can heighten the thermal insulation ability [108]. As the
Fig. 16 (b) shows the pore volume distribution of MOC/FSPCM porosity of composites increases, the interface area increases,
composites, and it exhibits that micropores between 0.01 and which improves the effect of interface thermal resistance and
0.1um account for the largest proportion of the voids, up to about reduces the density of the heat transfer network, resulting in a
80%, forming a channel for water molecules to enter, which is also decrease in thermal conductivity. Furthermore, the thermal con-
the reason for the poor water-resistance. Meanwhile, the increase ductivity decreases with the reduction of density because of the
of porosity can improve the insulation performance of materials, decline in heat transfer per unit volume.
literature [108] reveals that adding cenospheres into MOC cement
can increase the porosity, so that the heat preservation perfor-
mance is enhanced, and the strength and thermal conductivity of 4.2.5. Setting time
the material is inversely proportional to the porosity. The addition The setting time of MOC cement is divided into initial setting
of inorganic acids, such as tartaric acid and phosphoric acid, will time and final setting time, which are devoted to express the
slightly increase the porosity of MOC cement (Fig. 16 (c)) [73]. setting properties. The initial and final setting time is deter-
The small capillary pores (10–100 nm) occupy 71.9%, the highest mined by a vicat apparatus. The setting time is affected by both
proportion of the void (Fig. 16 (d)), which is similar to the MOC/ manufacturing craft and modifier. He [19] found that initial set-
FSPCM composites. ting time and final setting time both decreased with the increase
of mixing time at various stirring rates, and there is a linear
relationship between mixing time and setting time (Fig. 17(a)).
4.2.4. Thermal conductivity It also can be seen that the higher the stir rate, the shorter
Lightweight cement-based composites are often used as insula- the initial and final setting times. Guan [72] discovered that
tion materials, and thermal conductivity is considered to be a key the addition of citric acid made the setting times longer, and
property of such materials. Compositing materials with low ther- the influence got more obvious with the increasing dosage of
mal conductivity into composite can also improve the insulation citric acid (Fig. 17(b)).
performance. The thermal conductivity of FSPCM was lower than The influence of mixing and modifier on setting time can be
that of MOC cement, and with the increase of FSPCM content in explained from the hydration kinetics perspective. The increase
the composite, the thermal conductivity of MOC/FSPCM compos- of mixing time and stir rate tends to promote the neutralization
ites decreased significantly [110]. Air has the characteristic of reaction, so MOC cement slurry sets faster and the initial and final
super thermal resistance and very low thermal conductivity. The setting times become shorter. Water-resistant modifier, such as
 K. Li et al. / Construction and Building Materials 255 (2020) 119381 13

Fig. 17. Setting times of MOC cement: (a) the influence of mixing; (b) the influence of citric acid [19,72].

citric acid, has a retarding effect on MOC cement slurry. Thus, the cement is worthy of reference [114–116], which can be well
setting times are prolonged with increasing dosage of citric acid. applied to MOC cement.
Self-healing is another hot function of cement materials, and
the application in MOC has not been referred. For cement materi-
als, wrapping healing agent into hollow glass fiber (Fig. 19(a))
5. Future of MOC cement [117] and microcapsule (Fig. 19(b)) [118] are effective self-
healing strategies. The possible mechanisms of self-healing are
It has been more than 100 years since MOC cement was discov- summarized, as follows (Fig. 19(c)) [119]:
ered, but it has not been as widely used as Portland cement, mainly
because of the limitation of poor water-resistance. Only by solving 1) Formation of calcium carbonate or calcium hydroxide.
this problem, will MOC cement be well developed. The current 2) The crack blocked by particles falling off the side of the
modifiers can only improve the water-resistance in a limited crack.
way, but it is far from ideal. The research on the functionalization 3) Further hydration of the unreacted raw materials.
of cement-based materials is likely to provide a feasible path for 4) Expansion of the cementitious matrix in the crack.
the development of MOC cement, such as superhydrophobicity
and self-healing. Once self-healing of MOC cement is realized, the cracks can be
Bringing ultralow surface energies (10–20 mN/m) materials, timely blocked when the products are damaged, preventing the
like alkyl-based or fluorinated compounds, into cement, along with external water from contacting the phases 3 and 5.
the rough surface microstructure, the superhydrophobicity can be Besides, some new functions can be introduced into MOC
achieved [111]. However, so far, it is reported that only Gao et al. cement-based materials to enrich the application. The self-
[93] produced MOC cement with a superhydrophobic surface, but luminous cement [120], for example, can be contributed to decora-
they didn’t achieve the integral hydrophobicity of the material. tion and indication at night.
Room-temperature vulcanized fuoroalkylsilane (FAS) [112] and sil-
icone rubber (RTV) [113] are used as hydrophobic additives in
Portland cement (Fig. 18), and the fabricated samples are superhy- 6. Conclusions and recommendations
drophobic and mechanically stable. Even the scraped samples and
the cement powder still can exhibit superhydrophobic behavior. This review introduced various methods to improve the perfor-
The present study on the superhydrophobic properties of Portland mance of MOC cement, analyzed the modification mechanism, and

Fig. 18. Schematic diagram of the superhydrophobicity with different modifiers: (a) FAS; (b) RTV [112–113].
14 K. Li et al. / Construction and Building Materials 255 (2020) 119381

Fig. 19. Strategies and mechanisms of self-healing cement: (a) hollow glass fiber; (b) microcapsule; (c) possible mechanisms [117–119].

comprehensively described the macro and micro properties of research is to make phase 5 itself water-resistant without
MOC cement. The main points can be summarized as follows: reducing the other important properties.
2) The hydrolysis of unreacted MgO is also a significant reason
1) MOC cement is a sort of air-hardening gel material with for the poor water-resistance of MOC cement. Research on
excellent performance, but its poor water-resistance limits how to overcome the unwanted side effects of excessive
the development, hence, the water-resistance modification MgO is a key direction to improve water-resistance as well.
is the most important part of relative researches. 3) With the functional development of cement-based materi-
2) The properties of MOC cement-based materials can be com- als, it will become a trend to fabricate MOC cement with
prehensively characterized by micro and macro perspec- functions such as superhydrophobicity and self-healing,
tives. The change of micro structure, phases composition and the additional functions will certainly help overcome
will significantly reflect on the macro properties, such as the defect of poor water resistance.
strength and thermal performance. And taking good advan-
tage of various characterization methods is conducive to
better research and analysis of modified mechanism. Declaration of Competing Interest
3) The performance of MOC cement can be improved by con-
trolling raw materials, regulating the curing environment, The authors declare that they have no known competing finan-
adding modifiers and fiber reinforcement. Among them, cial interests or personal relationships that could have appeared
additives have the greatest influence on the water- to influence the work reported in this paper.
resistance of MOC cement, especially, the compound addi-
tives containing phosphate and polymer materials have the Acknowledgments
best effect.
This work was supported by the National Key R&D Program of
The advancement of new material technology will definitely China (Grant No. 2017YFC1104801) and the Key R&D Projects of
promote the building materials industry. With the continuous Sichuan Science and Technology Department of China (Grant No.
efforts of researchers, the research of MOC cement will surely enter 20ZDYF1408).
a new stage.
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