Desalination and Water Treatment 160 (2019) 14–22

August
www.deswater.com
doi:10.5004/dwt.2019.24189

Investigation of scale inhibitors effect on calcium carbonate nucleation process

Raghda Hamdia,*, Mohamed Tlilia,b

a
Laboratoire de Traitement des Eaux Naturelles, Centre des Recherches et Technologies des Eaux, Technopole Borj Cédria, BP 273
Soliman 8020, Tunisia, email: [email protected] (R. Hamdi)
b
Department of Chemistry, College of Sciences – King Khalid University, 9033 Abha, Saudi Arabia, email: [email protected] (M. Tlili)
Received 7 October 2018; Accepted 26 March 2019

ABST R AC T
Calcium carbonate precipitation has been studied for more than a century. Nevertheless, the early
stage of CaCO3 nucleation process still attracts the attention of researchers. In this paper, a new
method to investigate the effect of scale inhibitors on this nucleation is presented. It consists on the
modeling of the electrical conductivity evolution during CaCO3 precipitation by using a CO2-degas-
sing method called the fast controlled precipitation method (FCP). Tested inhibitors were sodium
polyacrylate (RPI) and sodium-tripolyphosphate (STP). Results shown that nucleation process is
governed by two main steps; in the first one ion pairs are formed by the association of Ca2+ and
CO32– ions. The second one consists on the agglomeration of the formed ion pairs to form stable nuclei
that can grow. Adding scale inhibitors slowed-down the nucleation rate and affects these two steps,
especially the ion pair agglomeration; the ion pair formation and precipitation threshold requires a
higher supersaturation coefficients showing that the inhibitor acts on the nucleation process by pre-
venting the association of calcium and carbonate ions and disrupting the aggregation of the formed
ion pairs. It was also shown that added chemicals inhibit the homogeneously formed CaCO3 nuclei
and affect the micro structure of the precipitate.

Keywords: Calcium carbonate; Scale inhibitor; Nucleation process; Ion pairs

1. Introduction (i) threshold effect, (ii) crystal distortion and (iii) dispersion.
The threshold effect is the ability of an inhibitor to prevent
Calcium carbonate scaling is at the origin of several
or to delay the precipitation of salts which have exceeded
technical problems in natural water installations: desalina-
their solubility products at a sub-stoichiometric level and to
tion plants, industrial cooling circuits, drinking water dis-
interact in non-stoichiometric ratios with nucleation sites to
tribution systems, etc. For this reason, a number of physical
limit the growth. Threshold inhibitors can also disrupt the
[1,2] and chemical methods for scale prevention have been
clustering and ordering processes but typically have little
developed. As chemical method, the inhibition of CaCO3
crystal distortion or dispersion properties. The crystal dis-
formation which consists on adding small amounts of min-
tortion affects the ordering and growth reactions. Interfer-
eral or organic chemicals is widely used in particular in
ence to normal crystal growth produces an irregular crystal
industrial circuits. So, a large range of inhibitory substances
structure with poor scale forming ability. The dispersion is
were shown efficient in the literature including phosphates
the ability of an inhibitor to reduce the agglomeration and
and phosphonates [3,4], polyacrylates [5,6] and various
the settling of suspended solids. The inhibitor chemisorbs
other polymers and copolymers of carboxylates and sulfon-
onto the crystal surface giving the crystal a surface charge.
ates [7,8].
Similar charges cause the crystals to repel one other.
Scale inhibitors function by one or more closely related
Several methods and analytical techniques have been
mechanisms interfering with the crystallization stages [9]:
used to highlight the mode of action of inhibitors. Liu et
al. [7] have used scanning electronic microscopy (SEM) and

*Corresponding author.

1944-3994 / 1944-3986 © 2019 Desalination Publications. All rights reserved.

 R. Hamdi, M. Tlili / Desalination and Water Treatment 160 (2019) 14–22 15

X-ray powder diffraction (XRD) to investigate the effect 2. Material and methods
of polymers. They showed that additives change highly
the morphology, micro structure and size of precipitated 2.1. Water preparation
calcium carbonate crystals. By using the field emission The calco-carbonic pure synthetic water CCPW was
scanning electron microscopy (FESEM), Ruiz-Agudo et al. prepared by dissolving 0.4 g·L–1 of solid calcium carbonate
[3] have proposed as inhibition mechanism, at the earlier in distilled water under CO2 bubbling according to:
stage of CaCO3 formation, that the additive hinders the
aggregation of pre-nucleation ions. Insufficient inhibitor CaCO3 + CO2 + H2O  Ca2+ + 2HCO3–
amount leads to an aggregation of pre-nucleation clusters
at higher supersaturation via amorphous intermediates
For all experiments, the initial pH value was adjusted
that later transform into crystalline phases. The formed
at 5.9 by CO2 babbling to maintain the work solution under
crystals grow through nonclassical oriented aggregation of
saturated [Ω = 0.25 Eq. (1)]. This supersaturation degree
nanoparticles that seem to incorporate the copolymer that
(Ω) with respect to calcite, which is the most stable form of
stabilizes them and prevents merging. This agree with the
calcium carbonate, is calculated considering the following
results of Al Nasser, et al. [10] which showed, using the
equation:
focused beam reflectance measurement (FBRM) inline mon-
itoring technique, that the inhibitory substance delays the  Ca 2 +  ⋅  CO 2-3  ⋅ γ Ca2+ ⋅ γ CO2−
CaCO3 clusters agglomeration. SEM images revealed that ΩCaCO3 = 3
(1)
K sp ( calcite )
the mechanism of inhibition could be a surface adsorption
or distortion of inhibitor molecules on the growing cal- where γi is the ion activity coefficient, [i] is the ion concentra-
cium carbonate crystals. Adsorption mechanism was also tion and Ksp(calcite) is the calcite solubility product.
proposed by Yang, et al. [11]. They demonstrated by using The ion activity coefficient, γi, was estimated using the
XRD, SEM and FTIR techniques that during CaCO3 crystal Davies equation:
growth, the inhibitor molecules or ions are adsorbed in a
 I 
different degree onto the various types of crystal faces, since log (γ i ) = − Azi2  − 0.3I  (2)
each type of face has a different surface lattice structure and  1 + I 
thus a different distribution of adsorption sites. Lin, et al.
where T is the temperature in K and ε is the dielectric
[12] proved, using a pH-stat system, that the presence of
constant of water which is calculated using Malmberg
inhibitors during precipitation can block the active growth
equation:
sites of the scale surface, thus retarding the growth stage
of calcium carbonate precipitation. Moreover Liu et al. [13]
showed, using the static and rapid controlled precipitation ε = 87.74 − 0.40008.T + 0.0009398.T 2 − 0.000001411.T 3 (3)
methods, that the inhibitors could distort the crystal lattice
of the precipitates, destroying their compact and regular and I is the ionic strength calculated according to:
crystal structures and changing them into loose and rough
1 n 2
ones, thus retarding the formation of precipitates. The SEM
and XRD analyses confirmed these findings. Greenlee et al.
I= ∑ci zi
2 i =1
(4)
[14] demonstrated that those inhibitors can also decrease where ci is the concentration and zi is the charge of the ith ion.
the mass of precipitated calcium carbonate by decreasing
particle size and modifying the shape of the precipitate.
These findings are confirmed by the SEM images. Such 2.2. Scale inhibitors
inhibitors are principally designed for their ability to form
a sufficient number of coordinative bonds with surface cat- Two well-known scale inhibitors, organic-sodium salt
ions of nucleating precipitates. That has been shown, using of polyacrylate (C3H3NaO2)n-and inorganic-sodium triphos-
Raman spectroscopy technique, in the case of inorganic phate (Na5P3O10)-called respectively thereafter RPI and STP
phosphate [15] and sodium polyacrylate [16]. were added in the reaction medium before the onset of the
A large variety of techniques were used to understand precipitation test. Small amounts, which have no significant
the mode of inhibitors action on calcium carbonate crystal- effect on the solution ionic strength and conductivity, were
lisation. Although the effect of inhibitory substances on the used. The concentrations of RPI used are 0.2, 4, 14 and 15
growth step and on the micro structure of CaCO3 is well ppm. Besides, the concentrations of STP used are 0.1, 0.6,
studied and several mechanisms were presented, few inves- 0.8 and 0.9 ppm.
tigations have focused on their effect at the nucleation stage. The structures of RPI and STP are shown in Fig. 1 and
So, the present work focuses on the effect of chemical sub- their physicochemical characteristics are represented in
stances on the CaCO3 ion pair formation and aggregation at Table 1.
the earlier nucleation stage. For this, our recently developed
method [17] for highlighting the role of CaCO3° ion pairs in 2.3. The fast controlled precipitation (FCP) experimental set up
the nucleation-growth of calcareous scale was exploited. As
inhibitors, polyacrylate and polyphosphate substances were The experimental set up of the fast controlled precipi-
tested. The method consists on modelling the precipitation tation (FCP) method is given in Fig. 2. The temperature of
curves (resistivity vs pH) by using the McCleskey model and the experiment was controlled with a water thermostat bath
considering thermodynamic calculations of all equilibrium maintained at 30°C. A polytetrafluoroethylene (PTFE) cell
between different species of CaCO3–CO2–H2O system. was filled with 500 ml of calco-carbonic pure water (CCPW)
16 R. Hamdi, M. Tlili / Desalination and Water Treatment 160 (2019) 14–22

Fig. 1. The structural formulas of scale inhibitors used.

Table 1 Ca2+ + 2HCO3– ↔ CaCO3 + H2O + CO2 dissolved ↑

The physicochemical characteristics of commercial scale
inhibitors used Degassing occurs on the interface air/water renewed by
magnetic stirring, which leads to an increase in the pH val-
Scale inhibitors RPI; sodium poly STP; sodium tripoly ues according to the following reactions:
acrylate phosphate
Molecular formula (C3H3NaO2)n Na5P3O10 CO2 dissolved ↔ CO2 atmospheric
Molecular weight 2000–2300 367.864
(g/mol) HCO3– ↔ CO2 dissolved + OH–
Appearance Clear, slightly White powder
yellow liquid In the FCP reactor CaCO3 precipitates both in bulk
Density (g/cm )3
1.15 0.8 solution and on the wall. At the end the FCP test, homo-
geneously formed precipitate (mb in gram) can be recuper-
pH 7.0–7.5 9.2–10.0
ated by solution filtration with a 0.45 mm pore size cellulose
Action with water Soluble Soluble nitrate membrane. By measuring Ca2+ amount remaining in
the solution, the total precipitated calcium carbonate mt can
be determined. The mass of calcium carbonate mw hetero-
geneously formed on the cell wall is then deduced (mw = mt
– mb) and its rate can be calculated as follow:

mw
% hete = × 100 (5)
mt

For each FCP test the efficiency is determined. It must

incorporate both the nucleation and growth phases. The
test time was therefore fixed. The scale inhibition efficiency,
E, was then defined by:

∫ (R − R0 ) dt − ∫ ( Rw − R0 ) dt
t t
wo
E(%) = 0 0
⋅ 100 (6)
∫ (R − R0 ) dt
t
wo
0

where R0 is the initial resistivity, Rwo and Rw are the resistivities

of water without and with inhibitor at time t, respectively.

Fig. 2. The fast controlled precipitation (FCP) experimental set

up. 2.4. Determination of the nucleation thresholds
The determination of the nucleation thresholds, indicat-
which was stirred at 800 rpm. The pH and the resistivity ing the beginning of each type of nucleation from a kinetic
of the solution were continuously recorded, by a pH-meter and thermodynamic point of view, is important given the
(Hanna HI 110), and by a conductivity-meter (Meter Lab fact that the formation of CaCO3 in water can take place
CDM210). The calcium ion concentration was measured by according to the two mode of nucleation (homogeneous or
EDTA complexometry titration. heterogeneous) [1,20,21].
The FCP method was the subject of numerous recent In order to better delimit the nucleation thresholds,
works [18,19]; its principle is therefore well detailed. It an in-situ measurement of solution conductivity during
consists in the displacement of the calco-carbonic equi- degasification by agitation was made. In Fig. 3 are reported
librium reaction towards calcium carbonate formation by experimental measurements of pH and resistivity ver-
degassing the dissolved carbon dioxide (CO2dissolved) from sus time of the solution during the precipitation process.
water. These measurements were carried out on 0.4 g·L–1 water
 R. Hamdi, M. Tlili / Desalination and Water Treatment 160 (2019) 14–22 17

Laxen [26] and McCleskey et al. [27] methods. Among

these models, it has been shown that the one proposed by
McCleskey et al is the most suitable for the conductivity
calculation. The methodology and basic steps of the curves
modelling have been described in detail elsewhere [17].
The electrical conductivity k of a solution for the McCle-
skey method is calculated as below:

k = ∑ λ i Ci (7)

where Ci is the ion concentration and λi is the ionic conduc-

tivity calculated as follow:
A (T ) I 1 2
λ = λ 0 (T ) − (8)
1 + BI 1 2
where λ0 and A are function of temperature (°C) and B is an
Fig. 3. Temporal evolution of (pH and resistivity) at 800 rpm, empirical constant.
30°C and CCPW0.4 g·L–1. The resistivity of the solution which is the reciprocal of
the electrical conductivity is calculated as below:

concentration, at 30°C temperature and 800 rpm stirring 1

Resistivity = (9)
speed. k
Fig. 3 highlights the limits between three zones: and
•฀ Zone 1: during the first ten minutes, until the prenucle-
∆ Resistivity = Resistivity (t ) − Resistivity ( 0 ) (10)
ation induction time “tprenuc“ is reached, pH increases
and resistivity remains constant. In fact the free ions
content does not change.
•฀ Zone 2: during the following forty minutes, between 3. Results and discussion
tprenuc and tprec (precipitation time), pH values still in 3.1. Effect of scale inhibitors on the nucleation threshold
increase with a small change of the resistivity variation
speed. The slope changing coincides with the equilib- Figs. 4 and 5 report the experimental measurements of
rium pH of calcite variety (Ω = 1.7 slightly higher than pH and ∆Resistivity during the precipitation tests in absence
1). The nucleation process becomes more rapid as soon and presence of RPI and STP. The most useful data are sum-
as the equilibrium compared to calcite variety, which marized in Table 2.
is thermodynamically the most stable one, is reached. The presence of scale inhibitors RPI and STP affects
Given the fact that the resistivity has only changed for remarkably the nucleation kinetic (Figs. 4 and 5). Indeed,
tprenuc increases from 12 min in absence of RPI to15 and 20 min
the pH exceeding the equilibrium pH of calcite variety,
in presence of 0.2 and 4 ppm of RPI (Table 2). Moreover, the
it can be confirmed that the clusters are formed by calci-
duration of the prenucleation step (∆t = tprec – tprenuc) increases
um and carbonate ionic associations such as ionic pairs from 34 min in absence of RPI to 40 and 190 min in presence
CaCO3° often evoked in literature [22,23]. of 0.2 and 4 ppm of RPI (Table 2). Thus the duration of the
•฀ Zone 3: being occurred until the end of the experiment. prenucleation step is longer as the inhibitor concentration
The slope of resistivity-time curve changes and the is higher. Consequently, the distinction between the prenu-
resistivity continues increasing rapidly. The related pH cleation and precipitation thresholds is easier. Liu et al. [28]
values decrease sharply after proton release and during proved that the nucleation was delayed after the addition of
crystalline growth. That is because after precipitation sodium polyacrylate. They supposed that the ionic associa-
CO2 formation speed is faster than CO2 degasification tion of the inhibitor have not interfered with the formation of
speed by agitation. At supersaturation has been reached CaCO3 clusters, but rather they protected them. Also, Clark-
(Ωprec = 48), it may appear a new wave of nucleation due son et al. [29] showed that in the absence of triphosphate there
to the formation of nucleus in important size in the solu- was a very short plateau indicating a rapid initial decrease in
tion which can justify the important change of the slope. free calcium concentration, but the presence of the inhibitor
increased the length of this plateau from 5 min (without tri-
Therefore, the in–situ measurements of solution resistiv- phosphate) to 30 min (with 10 ppm of triphosphate).
ity combined with those of pH during the precipitation pro- During the prenucleation step and for a concentration
cess, will be helpful in the present study to examine the scale of RPI ≤ 14 ppm and STP ≤ 0.8 ppm, a resistivity variation
inhibitors effect on calcium carbonate prenucleation stage. (∆Resistivity) is detected (Table 2). Indeed, ∆Resistivity increases from
65 Ω·cm in absence of inhibitor to 160 and to 189 Ω·cm in
presence of 4 ppm of RPI and 0.8 ppm of STP, respectively.
2.5. Conductivity modelling
It is therefore concluded that these substances, without com-
In a previous study, four conductivity calculation mod- pletely inhibiting the formation of ion pairs, act on their rate of
els are used: Kohlrausch [24], Jacobson and Langmuir [25], formation and consequently influence the nucleation kinetics.
18 R. Hamdi, M. Tlili / Desalination and Water Treatment 160 (2019) 14–22

Moreover, the chemical inhibition affects remarkably reaching high values for great amounts. Indeed the super-
the saturation state. As seen in Table 2, the supersaturation saturation coefficient reached in absence of inhibitor (Ωprec
coefficients increase as inhibitors addition increases until = 48) is multiplied by ~6 in the presence of 4 ppm of RPI
(Ωprec = 286) and in presence of only 0.6 ppm of STP (Ωprec
= 233). This can be explained by the fact that raising the
pH increases and subsequently the Ionic Activity Product
(IAP)”. The supersaturation coefficient, being equal to the
ratio of the IAP by the solubility product, increases with
the addition of the inhibitor. Consequently, the maximum
supersaturation reached at the initiation time of precip-
itation is not the direct cause of this precipitation but the
consequence of the operating conditions. Thus these sub-
stances inhibited the effect of supersaturation on the aggre-
gation rate of the CaCO3 clusters. This can be explained
by the fact that the germination requires a low rate of ion
pairs when the supersaturation is high. Thus, Table 2 shows
that the ∆Resistivity calculated at the precipitation threshold
increases with the amount of inhibitor added. Therefore
the metastable state breakdown requires the formation of
greater amount of ionic pairs in spite of the strong supersat-
uration. Since the presence of inhibitor can disadvantages
Fig. 4. Temporal evolution of (pH, ∆Resistivity) in absence and pres- the agglomeration and the coalescence of ions pairs and/
ence of RPI at 800 rpm, 30°C and CCPW0.4 g·L–1. or clusters, so that a nuclei can reach a critical size beyond
which it can grow up.
In addition to their influence on the nucleation thresh-
olds, scale inhibitors affect the adherence of scale on the
cell wall. Table 2 shows that the addition of each inhibitor
decreases the total precipitated calcium carbonate amounts
mt and increases the mass of calcium carbonate mw heteroge-
neously formed on the cell wall. Indeed, mt passes from 210
mg in the CCPW to 168 and 190 mg for only 4 and 0.6 ppm
of RPI and STP, respectively. Moreover mw passes from 94 mg
(%hete = 45%) in the CCPW to 133 (%hete = 79%) and 131 (%hete
= 69%) mg for 4 and 0.6 ppm of RPI and STP, respectively.
This scaling inhibition confirms previous results on calcium
carbonate nucleation obtained by degasification test [30].

3.2. Effect of scale inhibitors on the prenucleation stage

In order to have deeply insight into the effect of scale
inhibitors on the nucleation process and more precisely on
Fig. 5. Temporal evolution of (pH, ∆Resistivity) in absence and pres- the prenucleation stage, the resistivity vs pH curves were
ence of STP at 800 rpm, 30°C and CCPW0.4 g·L–1 modelled using the McCleskey model.

Table 2
Pre nucleation and precipitation time, supersaturation coefficients and heterogeneous percentage as a function of scale inhibitor
amount

Scale t prenuc(min) t prec(min) Ωprenuc Ωprec ∆ Resistivity mt (mg) mw (mg) % hete (%)
inhibitor (Ω·cm)
CCPW 12 46 1.7 48 65 210 94 45
RPI (ppm) 0.2 15 55 3 97 77 175 129 74
4 20 210 5 286 160 168 133 79
14 20 475 6 405 230 152 138 91
15 No precipitation detected
STP (ppm) 0.1 15 110 2.5 157 113 195 129 66
0.6 20 295 4 233 162 190 131 69
0.8 20 365 7 353 189 183 128 70
0.9 No precipitation detected
 R. Hamdi, M. Tlili / Desalination and Water Treatment 160 (2019) 14–22 19

During the prenucleation stage and as seen in Figs. CaCO3° formation is insignificant (Fig. 7). Given the fact that
6 and 7, the deviation of curves obtained after inhibitor the nucleation step is not achieved despite the formation of
addition from those of CCPW and McCleskey model starts a CaCO3° content close to that in the absence of inhibitor, we
as soon as the lowest pH values are reached. The prenu- can suggest that the role of STP is limited to reducing the
cleation pH has shifted from 6.73 in absence of inhibitor ion pair aggregation rate. Beyond this pH, a neat deviation
to 7.20 and to 7.11 in presence of 4 ppm of RPI and 0.6 between theoretical and experimental curves is recorded. This
ppm of STP, respectively. This means that added chemicals confirms that STP inhibits the association of Ca2+ and CO32–
delayed ion pair formation as well as higher supersatu- to form ion pairs. Such behaviour was observed with RPI at
ration coefficient was required; it has passed from 1.7 to lower pH values. The effect of RPI is then more significant on
5 and 4 in presence of 4 ppm of RPI and 0.6 ppm of STP, the inhibition of ion pair formation and aggregation (Fig. 6).
respectively.
Up to the precipitation pH recorded in absence of inhib-
itor (pH = 8.18), the effect of STP compared to that of RPI on 3.3. Effect of solution saturation state on the efficiency of scale
inhibitor
In the natural water distribution circuits, the supersatura-
tion coefficients remain too low compared to those obtained
at laboratory scale; except for the case of cooling towers where
degassing is intensive. Therefore, the optimization of an
inhibitor is dependent on a good knowledge of the thermo-
dynamic state of the water in the scaled circuit. It is in these
extreme conditions of precipitation (Ωprec > 353), at laboratory
scale, the content of RPI and STP scalants for a total inhibition
of precipitation is 15 and 0.9 ppm, respectively (Table 2). They
will be much less important to inhibit scale formation in a nat-
ural water circuit for the reasons cited above.
Thus, the experiments are carried out where the satura-
tion state of the water is controlled by stopping the degas-
sing of CO2 after solution isolation. All the precipitation
tests were conducted on 0.4 g·L–1 of CaCO3, at 30°C and
at 800 rpm in absence or presence of scale inhibitors RPI
and STP. At the beginning, the solution was brought to the
required pH, which is equal to 7.5 (Ω = 9.95), by magnetic
stirring. The cell was then closed hermetically in order to
limit CO2 transfers between liquid and gaseous phases;
Fig. 6. ∆Resistivity vs pH curves in the prenucleation stage calcu-
lated using McCleskey et al. [27] equation and obtained exper- equilibrium is almost established towards a pH 7.7 corre-
imentally in a FCP test as a function of RPI dosage at 800 rpm sponding to a supersaturation coefficient Ω = 15.77. Only a
and 30°C. slight pH increase of was recorded during the experiment.
The most useful data are summarized in Table 3.
Table 3 shows that at the same hydrodynamic condi-
tions and temperature, the CaCO3 precipitation is possible
at low supersaturation coefficients. Indeed for a CCPW, Ωprec
decreases from 48 to 20 after cell closing. For a 0.2 ppm of
RPI, Ωprec decreases from 97 to 33. And for a 0.1 ppm of STP,
Ωprec decreases from 157 to 128. Moreover the low supersat-
uration coefficients require longer time for a massive CaCO3
precipitation. Besides for a CCPW solution, the precipita-

Table 3
Pre nucleation and precipitation time, supersaturation coefficients
and heterogeneous nucleation percentage as a function of RPI
and STP dosages for a confined cell

Solution t prenuc t prec Ωprenuc Ωprec % hete

(min) (min)
CCPW 12 105 1.7 20 74
RPI (ppm) 0.2 15 390 3 33 97
1 –* – – – –
Fig. 7. ∆Resistivity vs pH curves in the prenucleation stage calculated STP (ppm) 0.1 15 440 3 128 82
using McCleskey et al. [27] equation and obtained experimen- 0.6 –* – – – –
tally in a FCP test as a function of STP dosage at 800 rpm and
30°C. *no precipitation
20 R. Hamdi, M. Tlili / Desalination and Water Treatment 160 (2019) 14–22

tion time of opened and confined cell was 46 and 105 min,
respectively; here, precipitation was delayed for 59 min.
After addition of 0.2 ppm of RPI, the precipitation time of
opened and confined cell was 55 and 390 min, respectively,
that is, the retarding time of precipitation was 335 min. For
treated water with 0.1 ppm STP, the precipitation time of
opened and confined cell was 110 and 440 min, respectively.
Precipitation was delayed for 330 min.
The precipitation is blocked at very low inhibitor dose
(1 ppm for RPI and 0.6 ppm for STP) when the cell is con-
fined (Table 3). Moreover, tprec for an opened cell and for 10
ppm of RPI is equal to 385 min, whereas for a confined cell
this same precipitation time is reached for only 0.2 ppm
of RPI (Tables 2 and 3). As a consequence the quantity of
added RPI is optimized 50 times. Besides, tprec for an opened
cell and for 0.83 ppm of STP is 450 min whereas for a con-
fined cell this same tprec is reached for only 0.1 ppm of STP.
Thus the quantity of added STP is optimized 9 times. This
proves that isolating the cell is very efficient to optimize the Fig. 9. Variation of the efficiency of inhibition vs. dosage of STP
quantity of inhibitor used. at 800 rpm, 30°C and CCPW0.4 g·L–1.
As shown in Fig. 8, after an addition of 0.2 ppm of RPI
(without cell-closing), the efficiency reaches 50% and from
8 ppm it occurs a blocking of the active sites of calcium car- after confining the cell, %hete for CCPW solution increases
bonate nucleus in growth until reaching 94% as maximum from 45 to 74%. For 0.2 ppm of RPI, it increases from 74 to
value of efficiency. It should be noted that the retarding 97 %. And for 0.1 ppm of STP, it increases from 66 to 82%.
effect of RPI, when the working cell is confined, occurs since Thus closing the cell orientates the adhesion of the formed
the addition of small quantity (0.2 ppm). Indeed the corre- nucleus of CaCO3 on the walls instead of their formation in
sponding affinity is equal to 94%. Besides, as seen in Fig. the bulk solution.
9, when the STP concentration was below 0.5 ppm for an The experiments show that a best optimization of scale
opened cell, poor inhibition efficiency was observed. When inhibitors used is reliant on a better thermodynamic knowl-
the dosage of STP was over 0.6 ppm, the efficiency reaches edge of water. As a result, the cost of treatment is reduced
maximum value of 95%. For a confined cell and up on addi- and the nature is preserved against these harmful sub-
tion of 0.1 ppm STP, precipitation of CaCO3 was almost com- stances.
pletely inhibited. To conclude, the effect of the two inhibitors
is more pronounced when the cell is confined because the
supersaturation coefficient, the aggregation speed and the 3.4. Effect of scale inhibitors on the nature of the precipitate
CaCO3° quantity are lower than those of the opened cell. formed
In addition, as seen in Table 3 the greatest heterogeneous In order to have more insight of the effect of each scale
percentages are reached when the cell is confined. Indeed inhibitor on the CaCO3 precipitation, the precipitate solid
obtained at the end of each FCP test was characterized
using the XRD technique. In Figs. 10 and 11 are presented

Fig. 8. Variation of the efficiency of inhibition versus dosage of Fig. 10. X-ray diffraction patterns of deposit scale at 30°C ob-
RPI at 800 rpm, 30°C and CCPW0.4 g·L–1. tained in absence and presence of RPI.
 R. Hamdi, M. Tlili / Desalination and Water Treatment 160 (2019) 14–22 21

of the two inhibitors is more pronounced when the cell is

confined because the blocking of calcium carbonate growth
nucleation was happened for lower dosage. Finally, on the
micro structural level, the presence of RPI favors calcite at
the expense of vaterite. However, the STP did not greatly
influence the micro structure of the formed scale.

References
[1] F. Alimi, M. Tlili, M.B. Amor, C. Gabrielli, G. Maurin, Influence
of magnetic field on calcium carbonate precipitation, Desalina-
tion, 206 (2007) 163–168.
[2] L. Zhu, Y. Han, C. Zhang, R. Zhao, S. Tang, Molecular dynam-
ics simulation for the impact of an electrostatic field and impu-
rity Mg2+ ions on hard water, RSC Adv., 7 (2017) 47583–47591.
[3] C. Ruiz-Agudo, C.V. Putnis, A. Ibañez-Velasco, E. Ruiz-Agudo,
A. Putnis, A potentiometric study of the performance of a com-
mercial copolymer in the precipitation of scale forming miner-
Fig. 11. X-ray diffraction patterns of deposit scale at 30°C ob- als, Cryst. Eng. Comm., 18 (2016) 5744–5753.
tained in absence and presence of STP. [4] H. Huang, Q. Yao, B. Liu, N. Shan, H. Chen, Synthesis and
characterization of scale and corrosion inhibitors with hyper-
branched structure and the mechanism, New J. Chem., 41
the XRD patterns of the precipitated obtained in absence (2017) 12205–12217.
[5] S.B. Ahmed, M. Tlili, M.B. Amor, H.B. Bacha, B. Elleuch, Cal-
and presence of RPI and STP. cium sulphate scale prevention in a desalination unit using the
The presence of RPI orientates the crystallization SMCEC technique, Desalination, 167 (2004) 311–318.
towards the formation of the calcite which becomes more [6] M.M. Tlili, A.S. Manzola, M. Ben Amor, Optimization of the
and more majority with increasing the inhibitor dose preliminary treatment in a desalination plant by reverse
whereas it is the vaterite that was favored in its absence. osmosis, Desalination, 156 (2003) 69–78.
In the case of precipitate formed in the presence of STP, [7] G. Liu, M. Xue, Q. Liu, H. Yang, J. Yang, Y. Zhou, Maleic anhy-
dride-allylpolyethoxy carboxylate copolymer as an effective
this inhibitor seems to not influence the phases formed; and environmentally benign inhibitor for calcium carbonate
vaterite remains the majority regardless of the STP content. in industrial cooling systems, RSC Adv., 7 (2017) 24723–24729.
These results may suggest that the modes of action [8] S.L.P. Wolf, K. Jähme, D. Gebauer, Synergy of Mg2+ and poly(as-
of these two inhibitors on the nucleation-precipitation of partic acid) in additive-controlled calcium carbonate precipita-
CaCO3 are different. tion, Cryst. Eng. Comm., 17 (2015) 6857–6862.
[9] E.G. Darton, Scale inhibition techniques used in membrane
systems, Desalination, 113 (1997) 227–229.
[10] W.N. Al Nasser, F.H. Al-Salhi, M.J. Hounslow, A.D. Salman,
4. Conclusion Inline monitoring the effect of chemical inhibitor on the cal-
cium carbonate precipitation and agglomeration, Chem. Eng.
In the present study, an accelerated scaling method, Res. Des., 89 (2011) 500–511.
based on electrical conductivity modelling applied to the [11] Q. Yang, Y. Liu, A. Gu, J. Ding, Z. Shen, Investigation of cal-
FCP method data, was used to assess the scale inhibitors cium carbonate scaling inhibition and scale morphology by
AFM, J. Colloid Interface Sci., 240 (2001) 608–621.
effect on calcium carbonate prenucleation stage. Tested [12] Y.P. Lin, P.C. Singer, G.R. Aiken, Inhibition of calcite precipi-
solutions are calco-carbonic pure waters. tation by natural organic material: Kinetics, mechanism, and
The presence of scale inhibitors RPI and STP affects thermodynamics, Environ. Sci. Technol., 39 (2005) 6420–6428.
remarkably the nucleation kinetic. Thus the distinction [13] D. Liu, W. Dong, F. Li, F. Hui, J. Lédion, Comparative perfor-
between the prenucleation and precipitation thresholds is mance of polyepoxysuccinic acid and polyaspartic acid on
easier for a higher dose of inhibitor. Indeed, the chemical scaling inhibition by static and rapid controlled precipitation
methods, Desalination, 304 (2012) 1–10.
inhibition increases the quantity of the nucleus formed and [14] L.F. Greenlee, F. Testa, D.F. Lawler, B.D. Freeman, P. Moulin,
thus the duration of each nucleation phase is prolonged. The The effect of antiscalant addition on calcium carbonate precip-
resistivity curves show that breaking the metastable state itation for a simplified synthetic brackish water reverse osmo-
requires the formation of larger amounts of ion pairs. This sis concentrate, Water Res., 44 (2010) 2957–2969.
suggests that the presence of the inhibitor delays the start of [15] M.M. Tlili, M.B. Amor, C. Gabrielli, S. Joiret, G. Maurin, P.
the agglomeration and the coalescence of ion pairs so that a Rousseau, Characterization of CaCO3 hydrates by micro-Ra-
man spectroscopy, J. Raman Spectrosc., 33 (2002) 10–16.
nuclei can reach a critical size beyond which it can grow up. [16] M.M. Tlili, Etude des mécanismes de précipitation du carbo-
In addition, these substances inhibited the role of supersatu- nate de calcium. Application à l’entartrage, in, University of
ration on the aggregation rate of the CaCO3 clusters because Paris 6, 2002.
the germination requires a low rate of ion pairs for high [17] R. Hamdi, M.M. Tlili, Conductometric study of calcium car-
supersaturations to take place. Moreover, the chemical inhi- bonate prenucleation stage: underlining the role of CaCO3o ion
bition promotes preferentially the heterogeneous nucleation pairs, Cryst. Res. Technol., 51 (2016) 99–109.
[18] Y. Chao, O. Horner, P. Vallée, F. Meneau, O. Alos-Ramos, F.
detrimentally to the scaling in the bulk solution. Besides, the Hui, M. Turmine, H. Perrot, J. Lédion, In situ probing calcium
inhibitors act to prevent the association of Ca2+ and CO32– to carbonate formation by combining fast controlled precipita-
form ion pairs. This effect is more marked with the organic tion method and small-angle X-ray scattering, Langmuir, 30
RPI inhibitor than that of the STP. Additionally, the effect (2014) 3303–3309.
22 R. Hamdi, M. Tlili / Desalination and Water Treatment 160 (2019) 14–22

[19] R. Hamdi, M. Khawari, F. Hui, M. Tlili, Thermodynamic and [25] R.L. Jacobson, D. Langmuir, Dissociation constants of calcite
kinetic study of CaCO3 precipitation threshold, Desal. Water and CaHCO3+ from 0 to 50°C, Geochim. Cosmochim. Acta, 38
Treat., 57 (2016) 6001–6006. (1974) 301–318.
[20] A. Fathi, T. Mohamed, G. Claude, G. Maurin, B.A. Mohamed, [26] D.P.H. Laxen, A specific conductance method for quality con-
Effect of a magnetic water treatment on homogeneous and het- trol in water analysis, Water Res., 11 (1977) 91–94.
erogeneous precipitation of calcium carbonate, Water Res., 40 [27] R.B. McCleskey, D.K. Nordstrom, J.N. Ryan, J.W. Ball, A new
(2006) 1941–1950. method of calculating electrical conductivity with applications
[21] M.B. Amor, D. Zgolli, M.M. Tlili, A.S. Manzola, Influence of to natural waters, Geochim. Cosmochim. Acta, 77 (2012) 369–
water hardness, substrate nature and temperature on het- 382.
erogeneous calcium carbonate nucleation, Desalination, 166 [28] J. Liu, S. Pancera, V. Boyko, J. Gummel, R. Nayuk, K. Huber,
(2004) 79–84. Impact of sodium polyacrylate on the amorphous calcium car-
[22] J.-Y. Gal, Y. Fovet, N. Gache, Mechanisms of scale formation bonate formation from supersaturated solution, Langmuir, 28
and carbon dioxide partial pressure influence. Part II. Applica- (2012) 3593–3605.
tion in the study of mineral waters of reference, Water Res., 36 [29] J.R. Clarkson, T.J. Price, C.J. Adams, Role of metastable phases
(2002) 764–773. in the spontaneous precipitation of calcium carbonate, J. Chem.
[23] D. Genovese, M. Montalti, F. Otálora, J. Gómez-Morales, M. Soc. Faraday Trans., 88 (1992) 243–249.
Sancho-Tomás, G. Falini, J.M. García-Ruiz, Role of CaCO3° [30] I. Ben salah, M.M. Tlili, M. Ben Amor, Influence of foreign salts
neutral pair in calcium carbonate crystallization, Cryst. to the CaCO3–CO2–H2O system and antiscalants on the adher-
Growth Des., 16 (2016) 4173–4177. ence of calcium carbonate on the stainless steel, Eur. J. Water
[24] F. Kohlrausch, The resistance of the ions and the mechanical Qual., 41 (2010) 51–66.
friction of the solvent, Proceedings of the Royal Society of Lon-
don, 71 (1902) 338–350.