Advances in Cement Research Advances in Cement Research, 2014, 26(2), 101–113

Volume 26 Issue 2 http://dx.doi.org/10.1680/adcr.13.00004

Paper 1300004
Characterisation of different commercial Received 09/01/2013; revised 20/04/2013; accepted 31/05/2013
reactive magnesia Published online ahead of print 03/09/2013

Jin and Al-Tabbaa ICE Publishing: All rights reserved

Characterisation of different
commercial reactive magnesia
Fei Jin Abir Al-Tabbaa
PhD candidate, Department of Engineering, University of Cambridge, Reader, Department of Engineering, University of Cambridge,
Trumpington Road, Cambridge, UK Trumpington Road, Cambridge, UK

Reactive magnesia (MgO) has emerged as an essential component in a new family of cements with significantly
superior technical and environmental performance over Portland cement. The physical characteristics of different
reactive magnesia, which are likely to affect their engineering performance, vary considerably depending on their
origin and manufacturing processes. To appropriately utilise such a material, it is essential to develop a better
understanding of the characteristics of different magnesia from various sources. In this study, the detailed
characterisation of 14 commercial magnesia in terms of reactivity, textural properties, X-ray diffraction pattern, pH
value and hydration behaviour and morphology is presented and correlation between them is developed. Relation-
ships were developed between the reactivity, specific surface area, agglomeration ratio and hydration rate based on
the experimental observations. As a result, the reactive magnesia used in this study were grouped into three
categories and their characteristics and anticipated performances in different applications were discussed.

Introduction filter cake that contains 50–72% magnesium hydroxide solids is

Magnesia (MgO) is an important industrial material for a wide
range of applications. It is produced from two main sources: (a)
‘naturally’ from magnesium-based minerals, in particular magne-
site and others such as dolomite and brucite, and (b) ‘syntheti-
cally’ from seawater, well and lake brines and bitterns and from
chemical precipitation (Kramer, 2001; Shand, 2006). When
magnesia is calcined from magnesite, the main reaction is
1: MgCO3 þ heat ! MgO þ CO2
heated to obtain magnesia
5: MgðOHÞ2 þ heat ! MgO þ H2 O
In synthetic chemical precipitation, magnesium compounds, such
as magnesium nitrate (Mg(NO3 )2 ) or magnesium sulfate (MgSO4 ),
are used to precipitate magnesium hydroxide, by adding base (e.g.
ammonium hydroxide) (Alvarado et al., 2000), from which the
magnesia is produced as in Equation 5 above.

If brine or seawater is the precursor, the reactions, which involve Generally, there are four grades of magnesia, depending on their
the use of lime, are (Shand, 2006) calcination temperature with different fundamental physical and
chemical properties.
2: CaO þ H2 O þ MgCl2 ! MgðOHÞ2 # þ CaCl2
j Light-burned (reactive or caustic-calcined) magnesia:
calcined at 700–10008C. It has the highest reactivity and
specific surface area (SSA) as well as the least crystallinity
CaO  MgO þ 2H2 O þ MgCl2 ! and has the lowest magnesia content due to the incomplete
decomposition of magnesite. Applications include catalysts,
3: 2MgðOHÞ2 # þ CaCl2
rubber and paper production and sulfur dioxide removal. The
applications for reactive magnesia have expanded in recent
years since it is widely used as a fertiliser/animal feed
CaO  MgO þ 2H2 O þ MgSO4 ! supplement, absorbent for inorganic/organic contaminants,
neutralising agent, filtration medium, cement and so on
4: 2MgðOHÞ2 # þ CaSO4 (Caraballo et al., 2009; Fukumoto et al., 2011; Garcı́a et al.,
2004; Jensen et al., 1986; Liska and Al-Tabbaa, 2008;
Rötting et al., 2008).
Dolomite is more often used instead of high-calcium lime as it j Hard-burned magnesia: calcined at 1000–14008C and has a
provides additional magnesia in the end product (Shand, 2006). correspondingly lower reactivity and SSA than reactive
After precipitation of the magnesium hydroxide (Mg(OH)2 ), a magnesia; this has been successfully used in China as an

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 Advances in Cement Research
Volume 26 Issue 2
expansive additive in concrete applications, particularly in
dam construction (Gao et al., 2008).
j Dead-burned magnesia (periclase): calcined at temperatures
of 1400–20008C and has an even lower reactivity and SSA,
as well as higher crystallinity. It is usually used in refractory
applications (Silva et al., 2011) and is one of the major
components in magnesium phosphate cements (Wagh, 2004);
it is also the type which is usually problematic in Portland
cement (PC) (Qian et al., 1998).
j Fused magnesia: produced at temperatures above the fusion
point of magnesium oxide (28008C). It is superior to dead-
burned magnesia in strength, abrasion resistance and
chemical stability (Canterford, 1985) with major applications
in refractory and electrical insulating markets.
For the reactive magnesia grade, the physical and chemical
properties, which vary considerably, are primarily governed by
the source of the precursor and calcination history. Alvarado et
al. (2000) prepared magnesia from various magnesium salts and
concluded that the SSA of the resulting magnesia decreased in
the following sequence: sulfate . nitrate . acetate . dolomite.
Aramendia et al. (1996) characterised reactive magnesia calcined
from brucite magnesium hydroxide and hydrated magnesium
carbonate (Mg5 (OH)2 (CO3 )4 .4H2 O) at 6008C and found that
those obtained from the former exhibited higher SSA and basicity
than those calcined from the latter. Numerous other studies
(Birchal et al., 2000; Cui and Deng, 2008; Eubank, 1951; Mo et
al., 2010; Sun et al., 1991) investigated the effect of the
calcination conditions, such as temperature and duration, on the
characteristics of the resulting magnesia, although the majority of
such work focused on magnesia produced from the same source.
They all agreed that with the increase of burning temperature
(include range studied) and/or burning time (include range
investigated), the SSA and the distortion of the crystal lattice
decreased and the particle size increased, resulting in decrease in
the reactivity of magnesia.
In contact with water, magnesia transforms to brucite, resulting in
expansion in the cement matrix, which is the main mechanism
for its shrinkage-reducing effect (Gao et al., 2008). The hydration
chemistry that involves magnesia and other cementitious materi-
als was summarised by Bakharev (2005), who claimed that in PC
paste, brucite is the most favoured product, whereas at high
reactivity (i.e. in the presence of fly ash, slag etc.), brucite is
usually accompanied with hydrotalcite, and magnesium silicate
hydrate (MSH) gel; however, they are essentially immiscible
owing to the basic structural differences between the nature of
ordered regions (Brew and Glasser, 2005). Numerous studies
were carried out and most of them confirmed the findings by
Bakharev (2005). Vandeperre et al. (2008a) reported that PC and
magnesia hydrated independently in the first month, whereas in
the study of Speakman and Majumdar (1971), ‘deweylite’, which
is defined as a poorly crystalline magnesium silicate hydrate, is
said to form naturally in hydrating Portland cements high in
magnesia. When supplemental cementitious materials are used,
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Characterisation of different commercial
reactive magnesia
Jin and Al-Tabbaa
interactions between magnesia and the other additives are
revealed and various hydration products are confirmed. Vande-
perre et al. (2008b) studied the microstructure of the magnesia
and PFA blends and observed brucite and a very small amount of
hydrotalcite (Mg6 Al2 (CO3 )(OH)16 (H2 O)4 ) from the X-ray diffrac-
tion (XRD) patterns, which is consistent with results by Ghanbari
Ahari et al. (2002), who reported the formation of hydrotalcite-
type phase on hydrating mixtures of alumina with reactive
magnesia. In the magnesia and silica fume blends, it was found
that magnesium silicate hydrate formed much more easily than
expected and the M/S ratio was less than 1 (Zhang et al., 2011),
which is consistent with the findings from Brew and Glasser
(2005), who successfully synthesised magnesium silicate hydrate
with varying ratios using chemical reagents.
The significant potential technical and sustainability credentials of
reactive magnesia in construction and environmental applications
emerged around a decade ago, following the development of
reactive magnesia cements (Harrison, 2008). Since then, extensive
on-going research at the University of Cambridge has confirmed a
range of significant advantages in a number of applications
including porous blocks (Liska and Al-Tabbaa, 2008; Liska, 2009;
Unluer and Al-Tabbaa, 2011), concrete (Li et al., 2010), ground
improvement (Jegandan et al., 2010), waste immobilisation, con-
taminated land remediation and wastewater decontamination (Cor-
tina et al., 2003; Iyengar, 2008; Rötting et al., 2006, 2008). In a
number of these studies in which magnesia from different sources
were used, differences in the performance were observed.
Owing to the different sources and production processes, the
characteristics and impurities in magnesia vary significantly,
which strongly affects its hydration kinetics and the interaction
with other cementitious materials. In order to effectively utilise
different reactive magnesia and to be able to specify applicable
ranges for certain physical and chemical properties, it is crucial
to develop an understanding of their characteristics, thus enabling
the evaluation of their performance in a range of different
applications. Hence, this paper presents a thorough characterisa-
tion of 14 different commercial reactive grade magnesia from a
range of different sources, many of which were already tested in
the applications listed above, to establish the relationship between
their basic characteristics such as reactivity, pH, SSA and
hydration behaviour. Eleven of the magnesia were calcined from
minerals, two synthesised from seawater and one was laboratory-
synthesised from chemical precipitation.
Materials and experimental methods
The sources and chemical compositions of the 14 commercial
reactive magnesia studied are shown in Table 1. The textural
properties (SSA, pore volume and mean pore radius) shown in
Table 2 were determined from nitrogen adsorption–desorption
isotherms on a TriStar 3000 instrument. The SSA was calculated
by the Brunauer–Emmett–Teller (BET) method, whereas pore
distributions were determined by the Barrett–Joynet–Halenda
(BJH) method.
 Advances in Cement Research Characterisation of different commercial
Volume 26 Issue 2 reactive magnesia
Jin and Al-Tabbaa

Source Supplier Label MgO CaO Fe2 O3 Al2 O3 SO3 B2 O3 Mn Na Cl SiO2 L.O.I.

Magnesite Causmag, Australia XLM 97.2 1.2 0.2 0.20 — — — — — 1.2 2.5
Premier Chemicals, USA Unimag 95.8 1.3 0.8 — — — — — — 2.1 NAa
RBH b , China 94/325 94.0 2.0 0.7 — — — — — — 1.0 2
RBH, China 94/200 94.0 2.0 0.7 — — — — — — 1.0 2
RBH, China 92/200 93.5 1.9 0.8 0.10 — — — — — 0.9 2.8
RBH, China 90/200 93.2 0.9 0.5 0.22 — — — — — 2.3 2.6
RBH, Greece 83CG 88.3 2.6 0.2 0.18 — — — — — 8.8 1.9
RBH, Greece 83CS 87.9 2.9 0.3 0.13 — — — — — 8.7 1.6
RBH, Greece NOR 91.6 1.7 0.1 0.14 — — — — — 6.5 2.3
RBH, Greece 83CR 88.9 2.6 0.2 0.15 — — — — — 8.2 2.2
Styromag, Austria K10 80.0 6.9 2.8 — — — — — — 6.0 7
Seawater Dead Sea Periclase, Israel DSP 99.2 0.2 0.01 0.004 0.125 0.005 0.04 0.1 0.02 0.8
RBH, China N50 97.7 0.5 0.03 — 0.8 — 0.002 — 0.1 — 5.4
Chemicals Intermag Ltd, UK IM 94.5 0.3 0.02 0.01 0.2 — — — 0.2 0.02 6
a
Not available.
b
Richard Baker Harrison Ltd, UK.

Table 1. Physical and chemical properties of magnesia in

percentage as provided by material supplier

Label SSA: m2 /g Specific pore volume: cm3 /g Average pore radius: nm GBET : nm GXRD : nm GBET /GXRD

XLM b 75.20 — — 22.19 16.4 1.4

Unimagb 79.90 — — 20.89 NM a —
94/325 16.31 0.11 26.50 102.33 43.0 2.4
94/200 4.37 0.01 10.06 381.92 53.0 7.2
83CG b 20.30 — — 82.22 30.9 2.7
3CSb 15.00 — — 111.26 35.1 3.2
NORb 24.30 — — 68.68 36.8 1.9
83CRb 47.80 — — 34.92 22.7 1.5
K10 29.13 0.18 22.47 57.29 22.6 2.5
DSP 144.93 0.25 5.98 11.52 11.1 1.0
N50 110.82 0.37 9.86 15.06 14.7 1.0
IM 118.26 0.24 6.18 14.11 12.3 1.2
a
Not measured.
b
Surface area obtained from datasheet.

Table 2. Textural properties and crystallite sizes of magnesia

The reactivity test was used to measure the time duration required
for the neutralisation of an acidic solution (in this case 0.25M
acetic acid) by a certain magnesia sample mass (in this case 5.0 g)
and phenolphthalein was adopted as the pH indicator (Shand,
2006). The time from adding the magnesia to the change of the
solution colour is recorded as the reactivity and the shorter the
time, the more reactive the magnesia is. The test was performed in
duplicate for each sample and the average value recorded.
The pH of the solution was measured using a Eutech pH510
integrated pH meter, with accuracy of 0.01. In this study, 10 g
of magnesia was added to a polyethylene bottle containing 100 g
of distilled water and then sealed and the pH of the solution was
measured, in duplicate, at different time intervals, from 1 to 90
days.
Thermogravimetric analysis (TGA) was employed to study the
hydration rate of magnesia. To hydrate the magnesia, the samples
were mixed with water at water/solid (w/s) ratio of 10:1 in
polyethylene bottles and sealed. The bottles were arbitrarily agitated

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 Advances in Cement Research
Volume 26 Issue 2
to ensure the solids did not settle at the bottom. The mixture was
sampled at different intervals and immersed in acetone for 3 days to
quench the hydration before being vacuum dried for at least 3 days.
The solid was then oven dried for 3 days at 808C to remove the
remaining water which is not chemically bound. The percentage of
magnesium hydrate was determined by heating to 8008C in the
DSC/TG machine (PerkinElmer STA6000). After obtaining the TG
curves, the first mass loss from 2008C to 4508C was attributed to the
decomposition of magnesium hydroxide (Alvarado et al., 2000).
XRD was employed to obtain the crystalline phases in the magnesia
samples and to calculate the crystallite size of the magnesia
particles. The specimens for analysis were obtained by vacuum-
drying, grinding and sieving. Each ground sample was mounted on
a flat holder and examined using a Siemens D5000 X-ray
diffractometer with a CuKÆ source operating at 40 kV and 40 mA,
emitting radiation at a wavelength of 1.5405 Å. The scanning
regions were between 2Ł values of 5 and 708, at a rate of 0.058/step.
The crystallite size, GXRD , was calculated using Scherrer’s
formula, using an X-ray diffractometer with CuKÆ radiation
6: GXRD ¼ Kº=  cosŁ
where º is the wavelength of CuKÆ (0.15405 nm),  the full-
width at half-maximum intensity (FWHM) of a Bragg reflection
excluding instrumental broadening, Ł the Bragg angle and K a
constant (¼ 0.9). As peaks at smaller diffraction angles are
desirable, the major characteristic peak of magnesia at 42.938
(2Ł) is used in the calculation (Chau and Li, 2008).
The primary particle size, GBET , was calculated using the
following equation, assuming that the particle shape was cubic
7: GBET ¼ 1000F=rS
where r is the theoretical density (¼ 3.595 g/cm3 ), S the SSA
(m2 /g) and F a particle-shape factor (¼ 6). A primary particle
does not always consist of a single crystal but often of several
crystallites whose average size is GXRD (Itatani et al., 1986).
GBET /GXRD is defined as the agglomeration ratio (AR).
The morphology of the particles was examined on the JEOL 820
scanning electron microscope (SEM) on gold-coated specimens.
Results and discussion
Composition and impurities
Table 1 shows the effect of the different origins on the chemical
composition of the different magnesia. The magnesia content
ranged from 80% to 99.2%; where the synthetic magnesia
generally had higher purity, with magnesia content of over 94%
for all three samples. The major impurities of calcined magnesia
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Characterisation of different commercial
reactive magnesia
Jin and Al-Tabbaa
are calcium oxide (CaO) and silicon dioxide (SiO2 ), which are
common minerals of rocks, whereas the major impurities of the
synthetic magnesia are calcium oxide, chlorine and sulfur trioxide
derived from seawater and chemical reagents.
The magnesia from RBH (Greece) had almost the same content
of calcium oxide but much more silica and much less iron oxide
compared to those from Causmag, Unimag and RBH (China),
attributable to the different compositions of the parent rocks. The
K10 magnesia from Styromag had the least magnesia content
(80%) compared to the other calcined magnesia and its silicon
dioxide and calcium oxide contents were both relatively higher,
indicating lower purity of the ore. The lower calcium oxide
content and higher sulfur trioxide content in the synthetic
magnesia indicates a lower pH value than those calcined.
Reactivity
The reactivity values of all the 14 magnesia powders tested are
plotted in Figure 1 and show that the synthetic magnesia, from
chemical precipitation and seawater, had the highest reactivities,
which were quite similar, whereas the magnesia calcined from
magnesite showed much lower reactivities and a much wider
range. This confirms that the reactivities of the calcined magnesia
are strongly affected by the thermal conditions of the calcination
(Birchal et al., 2000; Mo et al., 2010; Sun et al., 1991).
Textural properties
The textural properties of the magnesia powders are presented in
Table 2. The specific surface area values are plotted in Figure 2
and reveal that, although the synthetic magnesia have much larger
surface areas of 110–145 m2 /g, those for the magnesia calcined
from magnesite are much lower and range between 4 and 80 m2 /
g. It is also found that the specific pore volume, measured on
only six magnesia, increased as the SSA increased, whereas the
pore radius generally decreased. According to Rouquerol et al.
(1994), the pore system of all types of magnesia primarily
consists of mesopores (2–50 nm).
1000
Calcined
100
Reactivity: s
Synthetic
10
83CG
XLM
IM
Unimag
94/325
83CS
94/200
92/200
90/200
K10
N50
NOR
83CR
DSP
Figure 1. Reactivity of magnesia
 Advances in Cement Research Characterisation of different commercial
Volume 26 Issue 2 reactive magnesia
Jin and Al-Tabbaa

Synthetic 1000

140

120
BET surface area: m2/g

Reactivity: s
100 Calcined
100
80

60

40

20 10

0 0 20 40 60 80 100 120 140 160

BET surface area: m2/g
83CG
XLM

IM
Unimag

94/325

83CS
94/200

K10

N50
NOR
83CR

DSP

Figure 3. Relationship between specific surface area and reactivity

Figure 2. Specific surface area of magnesia

tions (Eubank, 1951). The relationship also reveals a drawback of

As shown in Figure 3, below a certain value of SSA (approximately
60 m2 /g in this study), the reactivity decreased remarkably with
the decreasing SSA. The result is consistent with the work by Mo
et al. (2010), who investigated the relationship between the
reactivity and SSA for magnesia from the same source but calcined
under different thermal conditions. They concluded that in addition
to the SSA, the hydration activity of the magnesia grains also had
an influence on the activity of the magnesia; the activity of
magnesia grains is related to the lattice structure and recrystallisa-
tion, which are determined by their source and calcination condi-
the acid test for evaluation of magnesia reactivity, since it is not
capable of distinguishing magnesia with very high reactivity.
Crystallite size and primary particle size
The XRD patterns of all the magnesia (excluding Unimag and 92/
200) are shown in Figure 4, which depict strong peaks for magnesia.
For those most reactive magnesia (namely, XLM, DSP, IM and
N50), peaks of brucite, at 2Ł ¼ 18.67 and 38.27, exist indicating
that these samples have hydrated to some extent by exposure to the
air. The characteristic peak of portlandite, at 2Ł ¼ 28.68, is present

XLM
94/325
94/200
90/200
83CG
83CS
NOR
83CR
K10
DSP
N50
DBG
Q B Q P MC B
10 20 30 40 50 60 70
2θ: degrees

Figure 4. X-ray diffraction curves for magnesia samples.

B: brucite, Mg(OH)2 ; M: magnesia, MgO; MC: magnesite,
MgCO3 P: portlandite, Ca(OH)2 ; Q: quartz, SiO2

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 Advances in Cement Research Characterisation of different commercial
Volume 26 Issue 2 reactive magnesia
Jin and Al-Tabbaa

1200
in K10, which is in agreement with its high calcium oxide content
(6.9%) (Table 1). Quartz is also detected in NOR, 83CR, 83CS,
1000
83CG and K10, agreeing well with their datasheets. The magnesite
present in 94/325 and 90/200 (2Ł ¼ 32.66) suggests incomplete
800
decomposition during calcination. Owing to the high purity of the

Reactivity: s
synthetic magnesia, the minor phases were not detected.
600
R 2 ⫽ 0·95
The calculated crystallite sizes of the magnesia are listed in Table
2. It is found that the crystallite sizes of the synthetic magnesia are 400
between 11 and 15 nm, whereas those of the calcined magnesia are
higher and vary between 16.4 and 53.0 nm, and are both in the 200
range of 10–200 nm reported by Itatani et al. (1993). It should be
noted that the results for the synthetic magnesia are in good 0
1 2 3 4 5 6 7 8
agreement with Aramendia et al. (2003), who synthesised magne-
Agglomeration ratio
sia from various chemicals and calcined the precipitated magne-
sium hydroxide at 6008C, suggesting the possible calcination Figure 5. Relationship between agglomeration ratio (AR) and
temperature of the synthesised magnesia in this study. The GBET reactivity (lower values means higher reactivity)
values for the synthetic magnesia were in the same range as the
GXRD values, whereas those for the calcined magnesia are much
higher in the range of 20–111 nm. 8: HD ¼ [L  (40=18)]=[(1  L)  C] 3 100%

Table 2 also shows that the agglomeration ratio (AR), defined as

GBET /GXRD , has values of ,1.0 for the synthetic magnesia. This
means that the crystallite sizes are almost in accordance with the
primary particle sizes and suggests that the primary particles are
composed of single crystals (Itatani et al., 1993). These values
are consistent with the laboratory-synthesised magnesia from
magnesium salts by Alvarado et al. (2000), although Itatani et al.
(1986) found that magnesia synthesised from seawater had AR
values of ,2 (calcined at 9008C). This suggests that the synthetic
magnesia used in this study were calcined at lower temperatures
(probably around 6008C, see above) than those used in Itatani et
al. (1986). For the magnesia calcined from magnesite, the degrees
of agglomeration were higher, in the region of 1.4–7.2, indicating
that they have larger primary particles consisting of more crystal-
lites.
The relationship between AR and reactivity results is illustrated
in Figure 5, which presents a good linear relationship
(R2 ¼ 0.95). The reactivity test in essence measures the hydration
time to achieve a certain hydration degree in the acid solution
and so it actually reflects the hydration rate of different magnesia.
Aphane et al. (2009) pointed out that the magnesia hydration
where HD, L and C represent the hydration degree, mass loss and
magnesia content in the sample respectively and the values of 40
and 18 are the molecular weights of magnesia and water, respec-
tively. The TGA curve of pure brucite is shown in Figure 6,
which shows that the mass loss is 30.24% between 2008C and
4508C, which is in good agreement with the theoretical value of
30.87%. For the TGA experiments, selective duplicate experi-
ments showed the standard deviation was within 2%.
Figure 7 presents the hydration rate of the different magnesia up to
90 days, which confirms earlier studies (Aphane et al., 2009; Liu
et al., 2007) that there is a limit for the hydration degree, which
varies between magnesia. The existence of the hydration limit
could be attributable to the incomplete hydration of the most
interior layer of single magnesia grains. Liu et al. (2007) reported
that for magnesia samples calcined from natural magnesite, the
100
95
Weight loss ⫽ 30·24%
90
85
Weight: %

process takes place with the product layered magnesium hydro-

xide causing stress leading to breakage, instead of continued 80
growth of the magnesium hydroxide layer. The lower the AR, the
75
quicker the magnesia hydrates to a certain degree, whereas for
those primary particles which contain several single crystals, the 70
particles need to be broken apart by the stress induced from the
65
brucite formed.
60
0 100 200 300 400 500 600 700 800
Hydration rate and degree Temperature: °C
The hydration degree of the magnesia was calculated from
Equation 8 according to sample mass loss owing to dehydration Figure 6. TGA curve for brucite
of magnesium hydroxide determined by TGA

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 Advances in Cement Research Characterisation of different commercial
Volume 26 Issue 2 reactive magnesia
Jin and Al-Tabbaa

100

XLM
80 94/325
94/200
90/200
83CG
Hydration degree: %

60
83CS
NOR
83CR
40
K10
DSP
N50
20 IM

0 10 20 30 40 50 60 70 80 90
Time: day
Figure 7. The degree of hydration of the commercial magnesia
tested

limit is around 70%. However in this study, it is found that many
of the commercial magnesia exceeded 80% hydration degree, and
the remaining magnesia were still hydrating after 90 days. It is
hypothesised that given enough time; the hydration degree of all
magnesia samples will reach the same point. The discrepancy
could be attributed to the fact that in both studies (Aphane et al.,
2009; Liu et al., 2007), the hydration time was only up to 24 days.
Figure 7 also shows that the synthetic magnesia almost reached
their limit within the first day, and hardly proceeded afterwards.
The fast hydration process of these synthetic magnesia is possibly
related to their larger pore volume (Table 3), as the diffusion of
water is facilitated by the high porosity.
The relationship between the SSA and the hydration degree at
1 day is shown in Figure 8. By excluding those magnesia, which
had almost reached their hydration limits (denoted by solid

Name/Symbol Source Reactivity: s SSA: m2 /g AR Category pH b

XLM Magnesite 19.5 75.20 NM a I 10.88

Unimag Magnesite 13.1 79.90 NM a I NM a
DSP Seawater 13.4 144.93 1.0 I 10.54
N50 Seawater 10.4 110.82 1.0 I 10.11
IM Chemicals 9.7 118.26 1.2 I 10.71
94/325 Magnesite 112.1 16.31 2.4 II 10.94
90/200 Magnesite 100.4 NM a NM a II NM a
83CG Magnesite 93.3 20.30 2.7 II 11.86
83CS Magnesite 226.3 15.00 3.2 II 12.06
NOR Magnesite 75.4 24.30 1.9 II 10.74
83CR Magnesite 31.1 47.80 1.5 II 11.11
K10 Magnesite 155.9 29.13 2.5 II 11.73
94/200 Magnesite 976 4.37 7.2 III 11.75
92/200 Magnesite 540.5 NM a NM a III 11.02
a
Not measured.
b
Based on 90 days’ data.

Table 3. Categorisation of magnesia in this study

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 Advances in Cement Research Characterisation of different commercial
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Jin and Al-Tabbaa

100 Hydration degree at 1 day magnesia are shown in Figure 9. It is clear that the equilibrium
90 pH of magnesia in solution was significantly affected by the
80 impurities present. At 56 days, all the pH values stabilised, with
the difference between 56 days and 90 days being less than 0.1
Hydration degree: %

70
R 2 ⫽ 0·87 unit. As the hydration proceeded with time, the pH values of all
60
the magnesia decreased by up to 0.6 units from the initial value.
50
In addition, although the bottles used in the experiments were
40 tightly sealed, it was unavoidable that during the process of
30 measuring pH, carbon dioxide in the air would have been
20 introduced and thus lowered the pH of the system. The equili-
10 brium pH value of portlandite (Ca(OH)2 ) (12.5) (Codina et al.,
2008) and brucite (10.5) (Shand, 2006) are also denoted on the
0
0 20 40 60 80 100 120 140 160 figure, between which most of the magnesia pH values lie,
BET surface area: m2/g because the major impurity in magnesia samples is calcium
oxide. The three synthetic magnesia showed the lowest pH values,
Figure 8. Relationship between specific surface area and 1 day which could be attributed to the sulfur trioxide present in the
hydration degree samples as well as the low calcium oxide content.

The relationship of the pH at 1, 28 and 90 days with the calcium

squares), the figure reveals that the hydration degree increases
linearly with the specific surface area, which is in accordance
with (Smithson and Bakhshi, 1969), who suggested that the
hydration degree is directly proportional to the SSA of the
magnesium oxide particles. A smaller SSA implies less surface
sites and less Mg2þ ions to go into solution to react to form
magnesium hydroxide, thus a slower hydration rate of magnesia.
oxide content is illustrated in Figure 10. It can be seen that the
pH values generally increased with the calcium oxide content up
to 3% until they reached the equilibrium pH of portlandite, after
which they stabilised. Although there is scatter owing to other
impurities present in the samples such as sulfur trioxide and other
alkalis such as sodium and potassium, it is clear that the pH value
is mainly controlled by calcium oxide content.

pH value
The pH is one of the important factors that control the perform-
ance of magnesia-based products in various applications such as
wastewater treatment, as neutralisation agent, and also in cemen-
titious materials. The pH developments up to 90 days of the
Microstructure
The morphologies of four typical magnesia, two calcined from
magnesite, one obtained from seawater and one from chemicals,
are illustrated in Figure 11. These show that the IM magnesia is
composed of agglomerates ,10 ìm in diameter, formed by grains

12·5

Equilibrium pH of calcium hydroxide

XLM
12·0 94/325
94/200
90/200
83CG
11·5 83CS
NOR
83CR
pH

K10
11·0 DSP
N50
IM

10·5

Equilibrium pH of Mg(OH)2

10·0
0 10 20 30 40 50 60 70 80 90
Time: days

Figure 9. Variance of the pH for magnesia in water

108
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 Advances in Cement Research
Volume 26 Issue 2
pH at 1 day
13·0 pH at 28 days
12·8 Equilibrium pH of calcium hydroxide
12·6 pH at 90 days
12·4
12·2
12·0
11·8
11·6
pH
11·4
11·2
11·0
10·8
10·6
10·4
10·2
10·0
9·8
0 1 2 3 4 5 6 7
Calcium oxide content: %
Figure 10. Relationship between pH and calcium oxide content in
magnesia
,0.3 ìm. The DSP magnesia is composed of uniform grains
,1–2 ìm in diameter with a very homogeneous distribution and
the magnesia grains not identifiable at the 10 000 times magnifi-
cation. The particles of the magnesia 90/200 are ,10–15 ìm in
diameter, while those of 94/200 at times exceed 20 ìm, which
indicates higher calcination temperature hence lower reactivity
than 90/200 (Itatani et al., 1986). The morphology study agrees
with the BET data; however, it also suggests that the traditional
acid test is not able to distinguish magnesia with very high
reactivity, as mentioned above (see Figure 3).
The SEM images of the hydration products of the four magnesia
cured for 1 and 90 days are shown in Figure 12. At 1 day, the IM
and DSP magnesia’ degree of hydration is .80% (Figure 7),
although their hydration products are quite different with a large
number of very fine hexagonal platelets of brucite formed on the
surface of the IM magnesia, whereas the DSP magnesia is
composed of larger irregular lamellas. No obvious morphology
changes were observed for the magnesia 90/200 and 94/200 at 1
day hydration. At 90 days of curing, the IM magnesia was still
covered by those hexagonal brucite platelets, but more lamellas
were identified, probably owing to the crystal growth and binding
of those platelets (Mo et al., 2010), and no change for the DSP
was found. For 90/200 and 94/200, the hydration products are
irregular grains which stacked closely and connected to each
other; these are 2–3 times larger than the unhydrated grains.
From the morphology study, it is found that the morphology of
brucite formed by magnesia varies between different magnesia,
which could be ascribed to the reactivity (Mo et al., 2010) and/or
the impurities (Henrist et al., 2003) in magnesia resulting from
their precursors and calcination history.
Classification of reactive magnesia
The findings in this paper show that characteristics such as pH,
reactivity, impurities, texture properties and morphology of
reactive magnesia from different sources vary significantly,
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Characterisation of different commercial
reactive magnesia
Jin and Al-Tabbaa
which is likely to influence the performance of reactive
magnesia-based products in various applications. The most
important two factors were identified as the impurities content
(or pH as an indicator) and reactivity, while the other charac-
teristics relate to those two. So far, the main work reported on
the link between the characteristics of reactive magnesia and
their performance has been confined to the catalysis field
(Aramendia et al., 1996, 2003; Teng et al., 2008) and little
relevant work has been conducted in the area of construction
materials. Chau and Li (2008) tested three light burnt magnesia
in magnesium oxychloride (MOC) cement pastes and revealed
the reactivity affects the setting time and strength development.
They reported that the magnesium oxychloride paste incorporat-
ing more reactive magnesia set faster and had higher early
strength; hence they classified light burnt magnesia into four
categories based on the reactivity test (Chau and Li, 2008).
Other than reactivity, there is very little mention in the
literature on the effect of other characteristics such as impu-
rities and SSA.
In PC–magnesia systems for applications in concrete (Li et al.,
2010) where MgO  PC, the calcium oxide impurity in the
reactive magnesia would not make much difference as its content
is very low and the pH is mainly controlled by the PC hydration
products. However, for applications in waste immobilisation (e.g.
of heavy metals or nuclear waste), the pH controlled by calcium
oxide content in the samples plays a significant role in the
solubility of metal hydroxides (Iyengar, 2008) and passivation of
aluminium (Zhang et al., 2011). For ground improvement,
although more reactive magnesia means higher early strength, it
may also cause fast setting and probably stuck the installation
equipment. For magnesia–slag or magnesia–microsilica systems,
both factors control the reaction kinetics as the pH determines the
solubility of aluminosilicate/microsilica and reactivity reflects the
availability of Mg2þ for reaction. In brief, to choose the appro-
priate magnesia, it is not only necessary to fully understand the
characteristics of magnesia, but also the system it will be put
into. Finally, a classification of reactive magnesia used in this
study is given in Table 3, mainly based on the reactivity results
j category I: highly reactive magnesia, with typical reactivity
value of less than 30 s, SSA over 60 m2 /g, AR less than 1.5
j category II: medium reactive magnesia with typical reactivity
value of less than 300 s, SSA over 10 m2 /g, AR less than 3.5
j category III: less reactive magnesia with typical reactivity
value of over 300 s, SSA less than 10 m2 /g, AR over 3.5.
For highly reactive magnesia, the hydration process almost
completes in 1 day, and the increase of SSA is not reflected by
the reactivity test. The high SSA and reactivity means faster
setting time and higher water demand in cements. For magnesia
that fall into the category II, the reactivity increases with the
increase of SSA and a hydration degree between 20 and 50%
is achieved in 1 day. Care should be taken when using
magnesia from category III as they hydrate very slowly, which
109
 Advances in Cement Research
Volume 26 Issue 2
(a)
(d)
(g)
Figure 11. Scanning electron microscope images of magnesia:
(a), (b) IM; (c), (d) DSP; (e), (f) 90/200; (g), (h) 94/200
would cause expansion at later age. As pH values are not
linked to reactivity, they are also listed in the table for
reference. The selection of specific magnesia by using this
table should be cautious as the performance of reactive
magnesia not only depends on the characteristics of magnesia
but also on the system into which they will be incorporated.
Conclusions
Characterisation of a wide range of reactive magnesia from
different sources and manufacturing processes was conducted in
terms of reactivity, textural properties, hydration degree and
hydrated pH value. It is found that the properties of the 14
commercial reactive magnesia varied significantly. In general,
synthetic magnesia showed higher purity and reactivity, larger
surface area, smaller crystallite size, smaller agglomeration ratio
and lower pH value compared to those calcined from magnesite
110
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Characterisation of different commercial
reactive magnesia
Jin and Al-Tabbaa
(b) (c)
(e) (f)
(h)
investigated in this study. In terms of relationships between those
characteristics, the following conclusions are drawn.
j The reactivity increases with the increase of SSA until SSA
reaches 60 m2 /g, after which the reactivity measured by acid
test does not change.
j There is a good linear relationship between the agglomeration
ratio and reactivity.
j A hydration limit exists for all the magnesia studied owing to
the incomplete hydration of the most interior area of
magnesia particles; it is found that the hydration degree
increases linearly with the increase of SSA before the
hydration limit is reached.
j The pH value of hydrated magnesia was primarily controlled
by the calcium oxide content in the samples. It can be seen
that the pH values generally increased with the calcium oxide
 Advances in Cement Research Characterisation of different commercial
Volume 26 Issue 2 reactive magnesia
Jin and Al-Tabbaa

(a) (b) (c)

(d) (e) (f)

(g) (h)

Figure 12. Scanning electron microscope images of hydration

products of MgOs: (a) IM hydrated for 1 day; (b) IM hydrated for
90 days; (c) DSP hydrated for 1 day; (d) DSP hydrated for 90
days; (e) 90/200 hydrated for 1 day; (f) 90/200 hydrated for 90
days; (g) 94/200 hydrated for 1 day; (h) 94/200 hydrated for
90 days

content up to 3% until they reached the equilibrium pH of Acknowledgements

portlandite.
Finally, based on the experimental results, it is recommended that
reactive magnesia can be divided into three categories, for
example highly reactive, medium and less reactive magnesia.
Characterisation of magnesia as well as the relationship between
those characteristics and performance of magnesia-based products
would facilitate the end-users to select the most suitable magnesia
for specific applications. The present work provides a preliminary
selection guide, and future work will focus on building the above-
mentioned relationship.
The authors express their gratitude to the Cambridge Overseas
Trust and China Scholarship Council for their funding of the PhD
studentship for the first author.
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