Key Engineering Materials Submitted: 2016-05-11

ISSN: 1662-9795, Vol. 712, pp 182-187 Revised: 2016-05-16

doi:10.4028/www.scientific.net/KEM.712.182 Accepted: 2016-05-23
© 2016 Trans Tech Publications, Switzerland Online: 2016-09-27

Waterproof Magnesia Binder for Composite Materials

Natalia A. Mitina1, a, Inna B. Revva1 , Alexander A. Ditts1, Dmitriy Simonov1
1
Tomsk Polytechnic University, 30, Lenin Avenue, Tomsk, 634050, Russia
a
mitinana@tpu.ru

Keywords: waterproof, magnesia binder, magnesium bicarbonates

Abstract. The paper presents a study of structure formation during the hardening of a new water
resistant hydraulic magnesium cement. Improvement of water resistance and the manifestation of
hydraulic properties in magnesium cement are associated with the use of a fundamentally new
mixing liquid involving a magnesium bicarbonate solution. Use of this solution makes possible for
the magnesium composition to harden not only in air, but also in water. The Coefficient of
resistance is 1.0–1.8. When mixing the magnesium cement with an aqueous solution of magnesium
bicarbonate, the main products of hardening are magnesium hydroxide and magnesium
hydrocarbonates. The increase of the hydrocarbon phase contributes to the strengthening
characteristics of magnesia compositions. Magnesium hydrocarbonates are insoluble in water,
which provides the increased water resistance of magnesia compositions and the opportunity to
harden and gain strength in water.

Introduction
Though it has many useful and unique properties, classical magnesium cement, mixed with
solutions of magnesium salts, is a cement with low water resistance, which limits its use in various
materials. The low water resistance of products based on magnesium cement is associated with the
formation of water-soluble crystalline hydrates – magnesium hydroxichloride
(xMg(OH)2•MgCl2•yH2O), which occurs when solutions of the corresponding magnesium salts are
used as a mixing liquid.
Different methods are used to improve water resistance, starting with changing the composition
and concentration of the mixing liquid of the magnesium cement, and the use of magnesium
chlorides and sulphates together [2, 3]. It was also found introducing ferric ions in the form of fine
iron ore with ferric iron oxide content to 65%, as well as a sol of iron hydroxide in the composition
of the modifying additive [4], into the cement paste, has a positive effect on improving the water
resistance of magnesium stone. Adding silicate magnesium rocks such as serpentine and diopside
also improves water resistance in magnesium cement [1, 5, 6, 7].
Improving water resistance is also possible through the interaction of atmospheric carbon
dioxide with magnesium hydroxychloride, resulting in the formation of a surface layer of
magnesium chlorocarbonate on crystalline particles Mg(OH)2·2MgCO3·MgCl2·6H2O [8], which
slows the leaching of the magnesium chloride from the cement [9].
These methods of increasing the water resistance of magnesium cement and the products thereof
do not preclude the formation of water-soluble substances in the hydration and hardening products,
as they were based on the use of magnesium salts as mixing liquids. A radical method to improve
the water resistance of magnesium cement involves synthesizing water-insoluble compounds in the
magnesium hardening products, which is possible only with the complete replacement of the mixing
liquid. Consequently, the mixing liquid plays a fundamental role in the composition of the
magnesium cement.
A principially new mixing liquid – a solution of magnesium bicarbonate was chosen as a result
of background research [10]. When mixing caustic magnesium powders with this solution, the
products of hydration of the magnesium cement have no water-soluble substances, what allows for
the conclusion that magnesium stone has increased water resistance and hydraulic characteristics.
When caustic magnesite interacts with an aqueous solution of magnesium bicarbonate, the first
proceeding reaction is the hydration reaction:

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 Key Engineering Materials Vol. 712 183

MgO + H2O → Mg(OH)2. (1)

A formed magnesium hydroxide interacts with magnesium bicarbonate resulting in the formation
of magnesium hydroxycarbonate hydrate and carbon dioxide:

Mg(OH)2 + Mg(HCO3)2 + 2H2O → MgCO3•Mg(OH)2•nH2O + CO2. (2)

Carbon dioxide resulting from (2) interacts with the excess of magnesium hydroxide forming a
secondary magnesium bicarbonate:

Mg(OH)2 + 2CO2 → Mg(HCO3)2. (3)

Secondary magnesium bicarbonate interacts with magnesium hydroxide according to the

reaction (2) with the formation of a new portion of magnesium hydroxycarbonate hydrate which
forms prime hydration products of magnesium cement with magnesium hydroxide. The products
ensure its hardening during recrystallization of prime colloidal products to the crystalline state.
The objective of this research is to study the structure formation of hardening of magnesium
cement using an aqueous solution of magnesium bicarbonate and its effect on properties of
magnesium compositions. For this purpose, it is necessary to define the structure of new formations
resulting from the interaction of magnesium powder with an aqueous solution of magnesium
bicarbonate and relation of the structure formation to the increasing hardening of magnesium stone
which are the primary objective of this paper.

Materials and methods

Materials
The object of the study is a magnesium cement of caustic magnesite mixed in a solution of
magnesium bicarbonate. Also, for comparison, tests were conducted on classical magnesium
cement in which a solution of magnesium chloride was used.
We used caustic magnesite of the brand PMK-75 on the basis of magnesite rock of the
Savinskoye field (Irkutsk region) with a content of active MgO 75.64 wt. % (Table 1). The caustic
magnesite was obtained by firing the magnesite rock at a temperature of 800°С at the company
LLC ‘Siberian Powders’ (Irkustsk).
Table 1. Chemical composition of caustic magnesite and source magnesite rock.
Material Content of oxides by weight [%]
MgO SiO2 Al2O3 CaO Fe2O3 MnO Δ mpr Total
Magnesite source 46.88 1.60 0.59 0.85 0.80 0.29 48.29 100
Caustic magnesite 75.64 3.18 0.62 4.24 0.83 0.32 16.85* 100
*- losses of caustic magnesite on ignition, calcined at 800 °С associated with the presence of
undecomposed MgCO3 with a defective structure.

A solution of magnesium bicarbonate Mg(HCO3)2 was obtained by artificial carbonation of

thinned MgO suspension at a pressure of carbon dioxide 9 atm in an autoclave at a temperature of
25°С [11]. In order to intensify the process of carbonization, an additive carbonate solution (caustic
soda) was used in an amount of 2.5% of weight of caustic magnesium powder. For a more effective
process flow, the autoclave was equipped with a stirrer, which stirred the solution immediately after
the gas was supplied. Carbonization time is 20 min. The concentration of the magnesium carbonate
solution was 19 g/l.
A solution of magnesium chloride MgCl2 was used with a density of 1.2 g/cm3.
184 Advanced Materials for Technical and Medical Purpose

Research methods
The phase composition of hydration and hardening products was determined by X-ray analysis.
The radiograms were obtained on a Shimadzu XRD 7000 diffractometer using Cu-anode radiation,
scanning step 2°/min, measuring time of the intensity of points in the scan 1 sec, tube voltage
40 kV, current 30 mA.
The structure of new growth and surface morphology of the samples was studied using a JEOL
6000 scanning electron microscope. The samples were captured under the following conditions:
accelerating voltage of the electron beam was 10-15 kV, working distance of the shot was 20-
50 mm with magnification of up to 10,000 times under low and high vacuum.
Plastic strength of magnesium cement samples with classical liquid mixing and with a solution
of magnesium bicarbonate at different hardening times was determined by a Rebinder cone-and-
plate rheometer with a cone angle of 60°.

Results and Discussion

The properties of materials and products based on the cementing materials, are directly
dependent on the structure and properties of the products of hydration and hardening. The process
of hydrating the magnesium cement is of a hydration-reactionary character, regardless of mixing
liquid applied, other than water. Thus, at the initial moment of interaction with caustic magnesite
salt solutions, hydration of MgO occurs to form Mg(ОН)2 according to the reaction (1). Next, MgO
or Mg(ОН)2 reacts with the anions of the dissolved salts to give the reaction products of hydrate
complexes.
When applying the solution of magnesium bicarbonate as a mixing liquid, the magnesium
hydroxide formed by reaction (1) reacts with the bicarbonate ions to form hydrocarbons of different
compositions. The magnesium bicarbonates have a crystalline structure of irregular crystals shapes
(barringtonite MgCO3·2H2O [14], lansfordite MgCO3·5H2O [U. Baumgärtl, 15]) to foliated plates
(hydromagnesite Mg5(CO3)4(OH)2·4H2O [U. Baumgärtl, 12]) and elongated columnar
(nesquehonite Mg(HCO3)(OH)·2H2O [15], dypingite Mg5(CO3)4(OH)2·5H2O [13]) crystals.
Optical study and X-Ray analysis
In order to establish the structure and phase composition of new growth during hydration of
magnesium cements, suspensions with a water-solid ratio of W/S = 10 were prepared to provide a
more complete flow of the hydration processes. The resulting suspension was sustained for 1 and
12 hours with constant stirring. Then the solid part of the suspension was separated from excess
liquid by filtering, and the solid residue was dried and disaggregated.
The results of electron microscope analysis (Fig.1, a) of the dried hydrated powders based on
caustic magnesite after 1 hour’s interaction with the magnesium bicarbonate solution, show the
presence of unreacted magnesium oxide particles, poorly crystallized amorphous masses of
magnesium hydroxide, as well as diverse columnar poorly crystallized formations of barringtonite,
which were supported by the X-Ray phase studies (Fig. 2, a). On the radiographs of powder
hydrated for 1 hour, the characteristic halo corresponding to the amorphous phase of magnesium
hydroxide and magnesium bicarbonate can be seen.
After 12 hours of hydrating the magnesium cement suspension with a solution of magnesium
bicarbonate (Fig. 1, 2, b) the crystallinity of the products of the reaction increases, but the presence
of an amorphous halo persists. At high magnification, foliated columnar crystals are detected,
collected in rosettes, which correspond to hydrocarbons of the hydromagnesite and dypingite type
[16, 17, 18]. These formations are in a poorly crystallized form and therefore do not appear on the
radiograph.
 Key Engineering Materials Vol. 712 185

Fig. 1. The structure of magnesium cement with a solution of magnesium bicarbonate: a) 1 hour of
hydration; b) 12 hours of hydration.

Fig. 2. Radiographs of magnesium cement with a solution of magnesium bicarbonate: a) 1 hour of

hydration; b) 12 hours of hydration.
Strength characteristics
Structural characteristics of new growth formed during hydration and hardening of cementing
compositions directly affect the strength characteristics of the cementing compositions, both during
the initial period of hardening, and the final strength.
In the initial period of hardening of magnesium cement (up to 12 hours), the cementing system is
characterized by plastic strength, which is determined on the Rebinder cone-and-plate rheometer by
immersion of the cone in a concentrated suspension of cement paste of normal consistency. For
comparison of strength properties of the resulting structures and the effect of the hardening
environment, caustic magnesite is mixed with an aqueous solution of magnesium bicarbonate and a
traditional mixing liquid – a solution of magnesium chloride.
Normal density of magnesium cement paste was, respectively: in the solution of Mg(НСО3)2 –
50 %, in the solution of MgCl2 – 35 %. Test results are shown in Fig. 3.
Study of the change of the plastic strength of magnesium cements (Fig. 3) during hardening
showed that the core setting of structural strength occurs in the first 5 hours.
186 Advanced Materials for Technical and Medical Purpose

Fig. 3. Dependence of plastic strength on the type of solvent and duration of hardening:
1 – magnesium cement mixed with a solution of MgCl2; 2 – magnesium cement mixed with a
solution of Mg(НСО3)2.

With a solution of magnesium chloride, a build-up of plastic strength of the cement paste occurs
more rapidly than with the use of a solution of Mg(НСО3)2. Within 2 hours, plastic strength values
reach values of 0.24 MPa. This level of plastic strength in magnesium cement with a solution of
magnesium bicarbonate is only reached after 3 hours of hardening. However, by 5 hours after
mixing, both compositions have practically the same level of plastic strength. After 5 hours the
hardening, the paste loses its plastic properties, and determining the level of plastic strength
becomes difficult. Next, we measured the samples’ compressive strength. Table 2 shows the
compressive strength of the samples of magnesium cement mixed with a solution of magnesium
chloride and a solution of magnesium bicarbonate. The samples formed after exposure to air for 1
day and hardened in different environments: air, air-humid conditions and water.
Table 2. Compressive strength of samples of magnesium cement.
Duration of hardening, Hardening environment Compressive strength, [MPa]
[days]
Solution of MgCl2 Solution of Mg(HCO3)2
0.5 Air 21 3.82
1 Air 25.8 7.64
3 Air 30.5 10.2
Air - humid 26.7 21
Water 20.1 32.4
14 Air 33.4 14.8
Air- humid 31.5 49.8
Water 20.1 53.8
28 Air 40.5 25.3
Air - humid 38.2 58.7
Water 28.3 63.2
Data on compressive strength show that the strength of samples of magnesium cement mixed
with magnesium chloride hardened in air is higher than when using a solution of magnesium
bicarbonate. However, an environment with higher humidity and water produces the opposite
effect. Hardening in water softens the magnesium cement on magnesium chloride, and magnesium
cement in a solution of magnesium bicarbonate shows good results in strength, reaching 63.2 MPa.

Conclusions
We can conclude from the studies conducted that when magnesium cement is mixed with an
aqueous solution of magnesium bicarbonate, the main products of hardening are magnesium
hydroxide and magnesium hydrocarbonates. The increase of the hydrocarbonate phase contributes
 Key Engineering Materials Vol. 712 187

to the increased strength characteristics of the magnesia compositions. Practically all kinds of
magnesium hydrocarbonates are soluble in water, which provides not only improved water
resistance of magnesia compositions, but also the opportunity to harden and gain strength in water.
A water environment contributes to a more intensive and complete flow of the process of hydration
and hardening of magnesium cement with a solution of Mg(НСО3)2, as there is a constant formation
of magnesium hydroxide, followed by its interaction with bicarbonate ions.
Obtaining waterproof and durable building materials based on hydraulic magnesium cement
makes their use possible in the construction of outer enclosing structures, waterworks, in the
production of paving stones, and when obtaining filling mortars and concretes.

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