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Journal of Crystal Growth 275 (2005) e1341e1347

www.elsevier.com/locate/jcrysgro

Assessing the effect of Mg2 on CaCO3 scale formationbulk

precipitation and surface deposition
Tao Chena,, Anne Nevillea, Mingdong Yuanb
a

School of Mechanical Engineering, University of Leeds, Leeds, LS2 9JT, UK

b
Baker Petrolite, 12645 W. Airport Boulevard, Sugarland, TX 77478, USA
Available online 23 December 2004

Abstract
The Mg2 ion, present in formation and injection waters is a key determinant in CaCO3 scale formation. The effect of
the Mg2 ion on scale formation is studied systematically in this paper, including aspects of the kinetics, habit and the
ratio of Mg/Ca in the scale. The kinetics of CaCO3 scale formation is studied both as precipitation in the bulk solution
and as deposition on a metal surface. Mg2 is shown to have a greater inhibition effect on bulk precipitation than
surface deposition. Detailed morphology analysis was used to understand the mechanisms of the inhibiting effect of
Mg2 on scale formation. Mg2 suppressed vaterite formation and the resulting scale was dominated by calcite.
Adsorption of Mg2 was observed on the crystals and this caused the roughness of the crystal surface to increase and
distortion of the crystals. The Mg/Ca ratio in the deposit is proportional to the concentration of Mg2 in the bulk
solution. The distribution coefcient in surface deposition and in bulk solution is a constant and independent of the
concentration of Mg2 ions in the bulk solution.
r 2004 Elsevier B.V. All rights reserved.
PACS: 01.10
Keywords: A1. Crystal morphology; B1. Calcium carbonate; B1. Magnesium

1. Introduction
Chemical scale formation associated with the
production of formation and injection waters can
result in oileld production problems that are
frequently expensive to remedy. Calcium carboCorresponding author. Fax: +44 113 242 4611.

E-mail address: mentc@leeds.ac.uk (T. Chen).

nate, CaCO3 ; is one of the most common scale

components found in oileld production wells and
surface facilities. Carbonate scale formation can
impair production by blockage of tubing and
owlines, cause fouling of equipment and can
conceal corrosion [1].
A variety of ions exist in formation and injection
waters, such as Mg2 ; Ba2 ; Sr2 ; Mn2 and SO2
4 ;
and it is well known that these can affect CaCO3

0022-0248/$ - see front matter r 2004 Elsevier B.V. All rights reserved.
doi:10.1016/j.jcrysgro.2004.11.169

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T. Chen et al. / Journal of Crystal Growth 275 (2005) e1341e1347

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growth rate [24]. Many of these ions have the

effect of inhibiting the growth of calcite. Although
many other ions are present in complex water
systems, Zhang [1,5] showed that the calcite
growth rate could often be well described by
considering inhibition from Mg2 only.
The nucleation rate as well as the crystal growth
rate of CaCO3 scale may be strongly affected by
the presence of Mg2 ions in formation water [6].
Many studies, using seeded growth tests, have
shown that the calcite growth rate can be inhibited
by the presence of Mg2 [2,79].
Few studies concerning the effect of Mg2 have
isolated the effects on bulk precipitation and
surface deposition. In the work reported herein,
the kinetics of CaCO3 scale formation are studied
both for scale precipitated from a supersaturated
bulk solution and deposited on a metal surface and
comparisons are given. Simultaneously, the habit
of crystals on the metal surface and the Mg/Ca
ratio of scale formed on the metal surface are
discussed.

2. Experimental procedures
Experiments were carried out at different Mg/
Ca ratios. The compositions of the solutions are
shown in Table 1. Calcium chloride (CaCl2 :6H2 O),
sodium chloride (NaCl), magnesium chloride
(MgCl2 :6H2 O), sodium bicarbonate (NaHCO3 )
used were of analytical grade supplied by BDH
Laboratory.
Experiments were carried out in a 800 ml vessel
thermostated at 20 1C. Six hundred milliliter scale
Table 1
Compositions of the solutions used for the effect of Mg2 on
scale formation

formation solution was used in each experiment.

CaCO3 was precipitated spontaneously by mixing
300 ml brine 1 (containing Ca2 ) and 300 ml
brine 2 (containing HCO2
3 ). The pH of brine 2
was adjusted to 6.8 by bubbling CO2 before
mixing. The pH of the scaling solution was
controlled at 6.7 by bubbling CO2 during the
experiments.
CaCO3 scales were deposited on the active
surface (+ 10 mm) of a rotating disk crystalliser (RDC) [10,11] made of stainless steel (UNS
S31603). Before immersing in the scale formation
solutions, the RDC was abraded with silicon
carbide paper to 1200 grit and polished afterwards
with diamond-polishing compound (6 mm). After
the nal abrasion, the specimens were rinsed with
distilled water and acetone and dried with
compressed air.
To study the effect of Mg2 on the kinetics of
scale formation, RDC samples are immersed in the
solution and rotated at 1500 rpm for 8 h. A
balance, with accuracy of 0.0001 g, is used to
measure the quantity of scale formed on the metal
surface after immersing in the scale formation
solution. Bulk precipitation is analysed by ltering
the solution after the experiment and measuring
the weight of the ltrate. Hence, both the quantity
of bulk precipitation and surface deposition are
quantied.
Scanning electron microscopy (SEM) was used
to analyse the habit of the scale crystals. Energy
dispersive X-ray (EDX) analysis was used to
analyse the composition of the surface deposit at
1500 rpm and to determine the ratio of Mg/Ca in
the scale.

3. Results and discussion

Mg2 concentration
(ppm)

200

400

600

3.1. Mg2 inhibition effect on kinetics of CaCO3

surface deposition and bulk precipitation

Mg2 =Ca2 ratio

Na (ppm)
Mg2 (ppm)
Ca2 (ppm)
Cl (ppm)
HCO
3 (ppm)

0
6873
0
1440
11,871
2196

0.227
6305
200
1440
11,579
2196

0.445
5738
400
1440
11,287
2196

0.667
5170
600
1440
10,995
2196

Fig. 1 shows the effect of Mg2 on surface

deposition. The quantity of surface deposit decreases with the increase of Mg2 in the solution.
At 600 ppm Mg2 ; a clear incubation period exists,
where no growth of CaCO3 is observed, and the
induction time is approximately 4 h.

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T. Chen et al. / Journal of Crystal Growth 275 (2005) e1341e1347
0ppm

200ppm

400ppm

600ppm

surface deposit (g)

0.004
0.0035
0.003
0.0025
0.002
0.0015

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different on bulk precipitation and surface deposition, although previous work [12] has shown that
chemical inhibitors can have different efciencies
when bulk and surface processes are considered.
This conrms the need to study both bulk
precipitation and surface scaling to completely
understand real industrial scaling processes [11].

0.001

3.2. Effect of Mg2 ion on habit of CaCO3 crystals

0.0005
0
0

10

time (hour)
Fig. 1. Effect of Mg2 on surface deposition under 1500 rpm
RDC.

efficiency (%)

precipitation

deposition

100
90
80
70
60
50
40
30
20
10
0
200

400

600

concentration of Mg in solution (ppm)

Fig. 2. Inhibition efciency of Mg2 on bulk precipitation and
surface deposition after 8 h at 1500 rpm.

In Fig. 2, the inhibition efciency of Mg2 on

bulk precipitation and surface deposition is shown.
Inhibition efciency is calculated as follows:
% inhibition efficiency Qa  Qp =Qa ;
where Qa is the quantity of scale in the absence of
Mg2 and Qp is quantity of scale in the presence of
Mg2 :
It is clear that both processes are inhibited by
Mg2 but to a different degree. In the presence of
200, 400 and 600 ppm Mg2 in the bulk solution,
the inhibition efciency is 30%, 41% and 69% for
surface deposition and 49%, 79% and 94% for
bulk precipitation. Mg2 ions apparently have a
greater inhibition effect on the bulk precipitate
than on surface deposition. It has not previously
been reported that the effect of foreign ions can be

To study the effect of Mg2 ions on the habit of

the initial layer of scale, experiments were carried
out under static conditions for 8 h. The habit of
CaCO3 during the crystal growth period was
monitored by post-test SEM examination. Fig. 3
shows SEM images taken after 8 h and there are
two kinds of crystal formed on the metal surface
under these conditions. These are apricot vaterite
and cubic or rhombohedral calcite. It is obvious
that the total number of crystals (vaterite and
calcite) decreases with the increase of Mg2
concentration in the bulk solution. In the Mg2 free solution (0 ppm), the crystals are mainly
vaterite and only few calcite crystals are observed.
In the 600 ppm Mg2 solution, calcite crystals are
predominant. The ratio of the amount of calciteto-vaterite on the metal surface increases as the
concentration of Mg2 in the solution increases.
Both perfect and distorted calcite crystals are
formed on the metal surfaces, as shown in Fig. 3.
The perfect calcite crystals are rhombohedral.
Whereas for the distorted calcite crystals, the edge
and the surface of the rhombohedral crystals are
distorted. In the 0 ppm Mg2 solution, all calcite
crystals are perfect. With the increase of Mg2
concentration in the solution, the percentage of
distorted calcite increases. In the 600 ppm Mg2
solution, all the calcite crystals are distorted.
In this study, Mg2 effects on the habit of
industrial calcite crystals are evident in two
aspects: on the crystal surfaces and at the crystal
edges. The effect of the Mg2 ion on the surface of
calcite crystals is shown in Fig. 4. At 0 ppm Mg2
solution, the surface of calcite crystals is smooth.
The surface becomes rough at 600 ppm Mg2
solution. Fig. 5 shows the effect of Mg2 on the
edge of calcite. In 0 ppm Mg2 solution, the edges
of the calcite crystals are perfect cubical or

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T. Chen et al. / Journal of Crystal Growth 275 (2005) e1341e1347

Fig. 3. Effect of Mg2 on the habit of surface deposits.

rhombohedral edges. In the Mg2 -containing

solutions, the edge of calcite crystal is rough and
growth steps are obvious. From a measurement of
the spatial distribution of the steps, some differences in step growth can be determined. As shown
in Fig. 5, 7 to 8 steps are observed in a 5 mm
distance in 200 ppm Mg2 solution and this is
reduced to 4 to 5 for every 5 mm in the 400 ppm
Mg2 solution and to 2 to 3 for every 5 mm in
600 ppm Mg2 solution. In the Mg-free solution,
homogeneous CaCO3 scale formed and the calcites
are perfect rhombohedral crystals. When Mg2
adsorbs on the calcite, heterogeneous MgCaCO3
scale formed, which could cause the distorted
calcite crystal formation [13].

Fig. 4. Effect of Mg2 on the surface of calcite crystals.

3.3. Mg/Ca ratio in surface deposition and in bulk

solution
Magnesiumcalcite scale is formed when Mg2
is present in the scale formation solution. Magnesiumcalcite interactions are strong because they
are enhanced by electrostatic interactions [14]. The
amount of Mg2 being adsorbed may be inuenced by the local solution chemistry and the
precipitation rate [1517].
The Mg/Ca ratio of surface deposit under
1500 rpm conditions is shown in Fig. 6. The Mg/
Ca ratio of surface deposit increases linearly as a
function of the concentration of Mg2 in the bulk
solution.

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T. Chen et al. / Journal of Crystal Growth 275 (2005) e1341e1347

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Fig. 5. Effect of Mg2 on the edge of calcite crystals.

natural systems [10]. In this study, the Mg/Ca

ratios in the solutions are 0.227, 0.445 and 0.667.
The Mg2 adsorbed on the scale is 0.63%, 1.44%,
and 2.04%, respectively; less than the 3% reported
by House [8].
The partitioning of magnesium between the
aqueous solution and the low magnesiumcalcite
in surface deposition may be quantied by dening
an distribution coefcient, D, as

ratio of Mg/Ca (mol/mol)

2.5
2

R2 = 0.9967

1.5
1
0.5
0
0

200
Mg

400
2+

600

in bulk (ppm)

Fig. 6. Ratio of Mg/Ca in surface deposit at 1500 rpm after 8 h.

Many Mgcalcites crystallise from solutions

with Mg/Cao1, e.g. in freshwaters. These minerals contains, in general o3 mol% Mg2 ; depending on the composition of the aqueous phase in

D fX Mg =1  X Mg g=fMg=Cag;
where X Mg is the mole fraction of Mg in the
surface deposition and (Ca) and (Mg) are the total
mole concentrations of calcium and magnesium,
respectively, in the bulk solution. The distribution
coefcient reects the distribution of the ratio of
Mg/Ca in the surface deposit and Mg/Ca ratio in
the bulk solution.

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T. Chen et al. / Journal of Crystal Growth 275 (2005) e1341e1347

In dynamic conditions (under 1500 rpm), the

distribution coefcient is 0.028, 0.033, 0.031 for
different Mg/Ca ratios of 0.227, 0.445, 0.667,
respectively, which is broadly in agreement with
the value of D 0:030  0:005 at 25 1C has been
determined by Howson [19] for Mg/Ca o1. It is
shown that the distribution coefcient is a
constant and is independent of the concentration
of Mg2 ions in the bulk solution.
When Mg2 ions are present in the scale
formation solution, they adsorb on the active sites
of CaCO3 crystals and cause three effects on scale
formation: (1) increase the solubility of calcite
[2,18,20]; (2) selective poisoning of crystal growth
sites [21]; (3) energy barriers will be increased
because of the size difference of Mg2 (0.65 A) and
Ca2 (0.99 A) [13]. These cause the inhibiting effect
of CaCO3 on both bulk precipitation and surface
deposition, as shown in Fig. 2.
In this study, CaCO3 bulk precipitation is
regarded as primarily a homogenous process
because the bulk solution is ltered before the
experiment, and calcium carbonate formed on the
metal surface is primarily a heterogeneous process.
Mg2 caused the distorted scale crystal formation,
which changed the adhesion ability of scale formed
on the metal surfaces and could cause the different
inhibiting effect on bulk precipitation and surface
deposition.
Calcite growth rate reduction in the presence of
Mg2 ions results from a decrease in the crystal
growth rate constant and follows a Langmuir
adsorption model, suggesting that the Mg2 ion is
adsorbed at growth sites on the crystal surface [6].
Paquette [9] suggested that there are geometrically
different types of surface sites on the original
surfaces of the calcite seeds. Mg2 has a higher
afnity for some of these sites and it is adsorption
or perhaps dehydration during incorporation that
preferentially slows down growth in specic
directions, for example towards the edges and
corners. This non-uniform adsorption of Mg2 on
the surface of calcite develops new crystal surfaces,
which have a higher Mg2 density and lower
growth rate than the original calcite seed surfaces
[5]. Consequently, new crystal faces will be
developed, and the type of surface sites for which
Mg2 has a higher afnity, eventually creating the

habit changes, dominates these faces. As shown in

Fig. 5, the growth steps appeared at the edge of
calcite crystals and the length of the growth steps
increased with the increase of the ratio of Mg/Ca
in the surface deposition. Also the surface roughness increased with Mg2 in the solution.
This study has contributed to the understanding
of the role of Mg2 in affecting calcareous deposit
formation from a supersaturated solution. Also,
through directing more attention to the scale
formation and adhesion at metal surfaces, in
parallel with precipitation processes, the entire
scaling process can be characterized.

4. Conclusions

Mg2 has greater inhibiting effect on bulk

precipitation than surface deposition at this
level of study, which shows that bulk precipitation and surface deposition are two different
processes and both processes should be studied
to completely understand an industrial scaling
system.
Mg2 suppressed vaterite formation and resulted calcite dominated scale. Mg2 adsorbs on
the surface of calcites causing the increase in
surface roughness and distortion of crystals.
Growth steps appear at the edge of calcite
crystals and the length of the growth steps
increases with the increase of Mg2 in bulk
solution.
Mg2 ions adsorb on the surface of deposit
crystals. The Mg/Ca ratio in the deposit is
proportional to the concentration of Mg2 in
the bulk solution. The distribution coefcient is
a constant and independent of the concentration
of Mg2 in bulk solution.

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