Desalination 249 (2009) 1397–1404

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Desalination
j o u r n a l h o m e p a g e : w w w. e l s ev i e r. c o m / l o c a t e / d e s a l

Efficiency of five scale inhibitors on calcium carbonate precipitation from hard water:
Effect of temperature and concentration
R. Ketrane a,b,⁎, B. Saidani a, O. Gil b, L. Leleyter b, F. Baraud b
a
Laboratoire de Technologie des Matériaux et Génie des Procédés/Equipe Electrochimie et Corrosion, Département de Génie des Procédés-Université de Béjaia, Route de Targa Ouzemmour,
Béjaia (06000), Algeria
b
Equipe de Recherche en Physico-Chimie et Biotechnologies (CORRODYS/ERPCB) -EA 3914-IUT/UFR Sciences — Université de Caen Basse Normandie, Boulevard du Maréchal Juin,
14032 Caen Cedex, France

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

Article history: The effects of temperature and concentration of five scale inhibitors (three polyphosphates, one
Accepted 24 June 2009 polyphosphonate and one polycarboxylate) on calcium carbonate (CaCO3) precipitation from hard water
Available online 8 October 2009 are reported in this paper. The CaCO3 precipitation from calcocarbonically pure water was induced by
imposed potential and studied on gold electrode by chronoamperometry technique. With this technique, the
Keywords:
efficiency of preventing CaCO3 precipitation was determined for all scale inhibitors. The composition of these
Hard water
scale inhibitors were analysed by ICP-AES technique and no or few toxic elements were detected. For each
Scale
Inhibitors
tested inhibitor, the optimal concentration was determined and their efficiency was studied in the range
Temperature temperature 20–50 °C. SEM/EDS and Raman spectroscopy techniques were used to analyse the
microstructure and the elemental composition of the formed scale. Only polyphosphonates remain efficient
at 50 °C. All the tested inhibitors were shown to act by threshold effect.
© 2009 Published by Elsevier B.V.

1. Introduction At more negative potential, water reduction reaction is also observed

[4].
Hard water generates adherent deposits of scale on the internal walls − −
of industrial or domestic equipments which cause severe technical 2H2 O þ 2e →2OH þ H2ðgasÞ ð2Þ
problems with a great economical impact. The clogging of pipes is the The presence of the hydroxide ions involves a local pH increase.
consequence of the scale formation which reduces heat transfer Then the following reaction below takes place [4].
efficiency, leading sometimes to the shutdown of an industrial plant
in the worst cases [1]. Increased energy and maintenance costs, as well − − 2−
HCO3 þ OH →CO3 þ H2 O ð3Þ
as plant shutdowns, are some of the economic penalties resulting from
scale deposition [2]. Scale is mainly constituted of calcium carbonate Finally, CO2−
content increase induces the precipitation of CaCO3
3

which has three crystalline forms [3]: calcite (rhombohedric structure),
aragonite (orthorhombic) and vaterite (hexagonal).
Scale deposition kinetics is generally long under natural conditions.
Therefore, different techniques have been proposed to accelerate the
phenomenon in the laboratory. One of them is the electrochemical
method proposed by Lédion et al. [4]. It consists of increasing the pH in
the vicinity of an electrode through an electrochemical reaction [4].
The principle is to cover with calcium carbonate a metal surface carried
to a fixed negative potential compared to a reference electrode [5]. The
application of this negative potential first involves, on the metal
surface, oxygen reduction reaction according to the equation [4].
− −
O2 þ 2H2 O þ 4e →4OH
⁎ Corresponding author. Laboratoire de Technologie des Matériaux et Génie des
Procédés/Equipe Electrochimie et Corrosion. Département de Génie des Procédés-
Université de Béjaia. Route de Targa Ouzemmour, Béjaia (06000), Algeria.
E-mail address: ketrane@yahoo.fr (R. Ketrane).
on the surface of the electrode.
2þ 2−
Ca þ CO3 →CaCO3ðSÞ ð4Þ
The formed deposit which is not conductive reduces the active
area of the electrode and constitutes a barrier for oxygen diffusion.
Then, the total cathodic current decreases and it can be followed by
chronoamperometric measurements. Characteristic chronoampero-
metric curves are obtained providing the scaling time (ts) reached
when the electrode surface is completely covered by the insulating
layer of CaCO3. The scaling time gives information about the scaling
power of a sampling solution [4]. This technique is widely used to
study CaCO3 precipitation and its prevention.
ð1Þ
Scaling can be prevented by physical and chemical techniques.
Antiscale magnetic treatment [6] and water treatment in electric
fields or the use of sonic waves [7] are physical techniques currently
used. However, the efficiency of these treatments is still controversial
as the involved phenomenon is not clearly elucidated yet [8].

0011-9164/$ – see front matter © 2009 Published by Elsevier B.V.

doi:10.1016/j.desal.2009.06.013
1398 R. Ketrane et al. / Desalination 249 (2009) 1397–1404
Chemical methods consist of adding chemical reagents like strong
acids, to lower the pH, or chelating agents, to complex Ca2+. But these
techniques are expensive and can have disastrous consequences on
the environment. In addition, the presence of metal cations as Zn+ at
low contents is sufficient to inhibit germination and growth of cal-
cium carbonate [9,10].
Chemicals for water treatment have been in use for more than a
century. Subsequent studies on the use of chemical additives for scale
inhibition have proven the efficiency of various polyelectrolytes on
retardation of crystal growth [11–14].
Threshold inhibition is the most appropriate method to control
scale crystal growth [15]. A widely used technique for controlling such
scaling problems is dosing trace amounts of chemical additives that are
able to inhibit growth of scale layer and weaken its adherence to a flow
surface. Significant scientific and technological efforts have been made
to control scale phenomena by adding small amounts (i.e. some g/m3)
of inhibitor agents [16,17]. Such low dosages are far from the stoichio-
metric concentration of the scaling species.
Chemical additives, known as “threshold inhibitors” reduce or
eliminate scale formation [18]. A large number of additive formulations
are commercially available. Commonly used antiscalants are derived
from three chemical families: polyphosphates, polyphosphonates and
polycarboxylic acids.
More than half of the drinking water treatment utilities in the
United States have adopted the use of phosphate-containing additives
[19]. The phosphates prevent the scale deposition by sequestering
calcium and inhibiting scale precipitation, even under conditions of
calcite oversaturation [20]. Threshold inhibition of calcium carbonate
formation by polyphosphates is particularly effective at a pH range of
8–10 in which carbonate scale in drinking water is a major problem. In
solution, linear polyphosphates undergo slow hydrolysis. Under
neutral pH and normal room temperature, this hydrolysis is relatively
slow. Higher temperatures will increase the rate of hydrolysis because
long chain polyphosphates will breakdown into shorter ones.
Phosphonates in various forms are also widely used to prevent scale
formation [17]. Polymer compounds with small molecular weight groups
as acryl and amino-acryl are frequently mentioned [20]. Characterized by
one or more functional groups (–PO3H2), these compounds contain
bonds P–C–P or P–C–N–C–P more stable than the P–O–P bonds of
condensed phosphates. The shorter the chains are, the better are their
adsorption and scaling inhibition. These molecules resist to hydrolysis
and have a greater effectiveness as scaling inhibitors. In addition, these
additives are used under stoichiometric quantities (threshold effect ac-
tion), contrary to the sequestering agents, this is economically interesting.
Polycarboxylic acids which have a cyclic or linear structural [18] are
other polyelectrolyte threshold inhibitors employed to reduce or elimi-
nate mineral scale formation. Some of the more familiar polycarboxylates
are: polyacrylic acid, polymethacrylic acid and polymaleic acid. Reddy
and Hoch [18] showed that inhibition of calcite crystal growth inhibition
by cyclic polycarboxyclic acids appears to involve blocking of crystal
growth sites on the mineral surface by several carboxylate groups.
Inhibition phenomena do not entail chemical reactions and stem
from complex physical processes, involving adsorption, nucleation and
Table 1
Main characteristics of commercial scale inhibitors used.
Scale inhibitor HMPS sodium MEDPHOS
hexametaphosphate
Nature Phosphate Polyphosphate
Formula (NaPO3)6 Na5P3O10
Density 2.18 1.1
pH 5.5–7.7 12.7
Aspect and colour White powder Colourless liquid
Action with water Soluble Hydrolize with water
crystal growth processes. The fundamentals of inhibition mechanisms,
particularly from their quantitative aspects, are poorly understood so
that the effects on inhibition effectiveness are largely unpredictable.
Generally, the mechanism suggested for the scale inhibition is
adsorption of antiscalant on the crystal surface, which blocks the
active crystal growth sites. After the adsorption phase, several modes
of actions are considered: delaying germination, slow down crystal
growth rate, favoring homogeneous germination on the detriment of
heterogeneous germination or deforming the crystals, giving them a
friable structure that weakens its adherence to a flow surface.
There is large information available in the literature about the
precipitation and the effects of inhibitors on scale kinetic [17,18,21,22].
On the other hand, few studies compare the efficiency of polypho-
sphates, polyphosphonates and polycarboxylic acids used under the
same conditions, and few investigations are devoted to the cross effect
of temperature and inhibitors.
In this work, the inhibition of calcium carbonate precipitation by five
commercial scale inhibitors (three polyphosphates, one polyphosphonate
and one polycarboxylic acid) was studied. The efficiency of these inhibitors
on CaCO3 precipitation from calcocarbonically pure (CCP) water was
determined with a gold electrode by a chronoamperometry technique. The
combined effect of water temperature and inhibitor concentration was
investigated. The precipitate morphology was examined by scanning
electron microscopy (SEM). The main elements are identified by energy
dispersive spectroscopy (EDS) technique and Raman spectroscopy.
In the semi arid areas, the main part of water requirements is
ensured by groundwater and geothermal water. The lifespan of the
water drainpipes in these areas is very limited in time because of the
strong water hardness and the high temperature. The present study
on the inhibitors scaling could find a good application for geothermal
water where the water temperature can reach 50 °C.
2. Experimental
2.1. Water preparation
The experimental solution is calcocarbonically pure water (CCP
water) containing only Ca2+, CO2− 3 and HCO− 3 ions in order to avoid
any side effect by foreign ions. This hard water is then of 30 °F (1 °F
corresponds to 10 mg L− 1 of dissolved CaCO3) which. The CCP water
was prepared by dissolving 0.3 mg L− 1 CaCO3 reagent grade in
deionised water. A pH solution of 5.7 is then obtained by bubbling CO2
during 10 h, according to the reaction.
2þ −
CO2 þ H2 O þ CaCO3 →Ca þ 2HCO3 ð5Þ
2.2. Characterization of scale inhibitors
To prevent CaCO3 precipitation, three polyphosphates (HMPS,
MEDPHOS and STTP), one polyphosphonate (SECAL) and one poly-
carboxylic acid (RPI2000) were tested. All these antiscalants are
commercial chemical additives whose exact composition is unknown.
This constrained us to reason according to the physical nature of
STTP sodium tripolyphosphate SECAL RPI2000 sodium
polycarboxylate
Polyphosphate Phosphonate Polyacrylate
Na5P3O10 68.8% phosphate + Phosphonates + =(C2H3COONa)−n
25.3% phosphorure dispersing polymers +
aqua (>50%)
0.8 1.11 1.155
0.5–7.7 10.3 /
White powder Yellow liquid clearly Colourless liquid
Soluble Miscible in any proportion Soluble
 R. Ketrane et al. / Desalination 249 (2009) 1397–1404 1399

Table 2
Analysis of the different scale inhibitors by ICP-AES technique.

Element Ca Mg K Na P S Al As Cd

Solid compound (mg g− 1)

HMPS 0.056 0.007 0.364 44.506 72.815 0.125 0.019 – –
STTP 0.022 0.059 1.703 44.031 65.533 5.590 0.225 0.002 –

Liquid compound (mg L− 1)

SECAL 22.01 4.01 125.41 15,643.21 10,674.81 5.16 4.86 0.07 0.01
MEDPHOS 482.57 14.09 192.74 19,342.06 10,827.73 409.42 43.27 0.19 –
RPI2000 9.73 1.37 25.20 19,447.90 414.01 8862.53 0.21 0.18 –

Element Cr Cu Fe Mn Pb Ni Se Si Sn Sr Ti Zn
−1
Solid compound (mg g )
HMPS 0.008 – 0.012 – – 0.001 – 0.044 – 0.001 0.005 0.009
STTP 0.005 – 0.013 – – – – 0.071 – – – 0.065

Liquid compound (mg L− 1)

SECAL 0.28 – 0.22 0.02 – 0.03 – 50.33 0.06 0.33 0.00 0.15
MEDPHOS 0.47 0.02 0.36 0.32 0.41 0.06 0.23 2750.90 1.00 1.32 0.21 0.58
RPI2000 0.03 0.12 0.00 0.01 – – 0.22 44.26 0.16 0.06 0.00 0.04

the product (liquid or solid) in the estimate of the added antiscalant sample. Electrons impact produces a characteristic X spectrum emis-
quantities. Their main characteristics are reported in Table 1. sion, which allows a local analysis with a space resolution better than
In order to determine the elemental composition (especially toxic the µm2.
heavy metal contents) of the commercial scale inhibitors used, they Micro-Raman analyses were performed on a Jobin Yvon High Reso-
were analysed by ICP-AES (Inductively Coupled Plasma - Atomic lution Raman spectrometer (LabRAM HR) equipped with a microscope
Emission Spectrometry) technique. The analysis was performed with (Olympus BX 41) and a Peltier-based cooled charge coupled device
a Varian Vista MPX. (CCD) detector. The analysed zone had a diameter of about 5 μm. Spectra
No significant level of toxic elements was detected in the inhibitors were recorded with the acquisition LabSpec software at room
(Table 2). temperature with a resolution of about 2 cm− 1. Excitation was provided
by a He–Ne laser (632.8 nm) and laser power varied between 1.94 and
2.3. Precipitation test 0.07 mW in order to prevent an excessive heating that could induce
sample modification and to avoid fluorescence of certain particles.
In order to evaluate the scale inhibitor efficiency, calcium
carbonate precipitation was induced by an electrochemical technique. 3. Results and discussion
A classical three-electrode cell was used. Its double glass wall allows
setting the temperature of the solution in the range of 20–50 °C. Its 3.1. Preliminary tests
large volume (250 mL) avoids concentration variations during the
deposit formation. Preliminary precipitation tests were carried out in CCP water of
The three electrodes used are: a work electrode of gold disc of 30 °F hardness without scale inhibitors.
0.196 cm2 area, a saturated calomel electrode (SCE) as reference Fig. 1 shows the i = f(E) curve obtained for various temperatures
electrode and a platinum grid as counter electrode. The tests were run on a gold rotating disc 700 rpm in CCP water of 30 °F hardness with
on rotating disc electrode (RDE) with a rotation speed of 700 rpm for scanning rate of 5 mV s− 1. The shape of the curve is in conformity with
all experiments. To study scaling on a gold electrode, it is necessary to
apply a cathodic potential of − 1 V/SCE, corresponding to the
dissolved oxygen reduction [22]. The gold electrode is previously
immersed in an acetic acid solution at 0.5 M during 5 min [22] then
rinsed with distilled water, and finally wiped with absorbing paper. In
order to ensure result reproducibility of scaling, in particular at the
initial moments, a cathodic pretreatment at − 2.5 V/SCE is applied
during 10 min. This processing eliminates species that partially block
the surface, through hydrogen release [22,23]. However, this
operation was not done in the presence of inhibitors to avoid their
possible decomposition at strong cathodic polarizations.
Electrochemical experiments were driven under potentiostatic
conditions using a RADIOMETRE PGP 201 interface (Potentiostat/
Galvanostat (PG)). A computer provided with a Windows software
application (Voltamaster1), controls all the functions of the interface.
Characteristic chronoamperometric curve i =f(t) could then be
obtained, providing that the scaling time (ts) is reached when the
electrode surface is completely covered by the insulating layer of CaCO3.
Ex-situ characterization of calcareous deposits was performed
with a Cambridge S240 scanning electron microscopy (SEM) which is
equipped with a probe of analysis by X energy dispersion (EDS) which Fig. 1. Voltamperometric curves obtained on gold electrode at 700 rpm in CCP water of
allows the determination of the elements nature present in the 30 °F hardness for different temperatures.
1400 R. Ketrane et al. / Desalination 249 (2009) 1397–1404
what is reported in the literature [24]. The diffusion stage related to
the dissolved oxygen reduction is observed; it disappears in solution
free oxygen. OH− ions result from a cathodic reduction of the
dissolved oxygen in the water (Eq. (1)). At more cathodic polariza-
tion, an intense hydrogen release due to the water decomposition
reaction (Eq. (2)) is observed. Although the solubility of dissolved O2
decreases with the temperature, Fig. 1 shows that the currents
increase proportionally with temperature. The increase of the
currents is explained by the effect of thermal agitation and by two
other combined effects: the decrease of solution viscosity and the
increase of the diffusion coefficient. Indeed, Kunjapur et al. [25] have
shown that the reduction reaction of O2 (Eq. (1)) is accelerated by a
temperature increase. Thus, for electrochemical scaling tests in
temperature range of 20–50 °C, the potential E = −1 V/SCE seems
adequate. At this potential, for all temperatures, the reaction of
oxygen is sufficiently developed to give interfacial conditions of pH for
precipitation. Moreover, for these conditions, hydrogen gas evolution
is not very developed.
The chronoamperometric curves i = f(t) obtained at 20 °C (Fig. 2)
under the same previous experimental conditions show a strong
cathodic current at the very beginning, then a stage is observed and
the residual current tends towards zero value. The average time
scaling recorded is 35 min. The current values recorded at t = 0 min at
20, 35 and 50 °C are respectively − 0.52, − 0.75 and − 0.93 mA cm− 2
(Fig. 2). This behavior is explained by the activation of the cathodic
reactions (Eqs. (1) and (2)) with respect to temperature in agreement
with previous curves (Fig. 1). For higher temperatures, the current
presents a sudden fall at the beginning of experiments, and then a
stage and the residual current tends to zero. For experiment at 20 °C
we observed the same current fall behaviors but only after an initial
scaling time of about 20 min. As expected, we also notice that the
higher the electrolyte temperature is the shorter the scaling time is.
Indeed, the scaling time that was 35 min at 20 °C, is 25 min at 35 °C
and finally decreases to 10 min at 50 °C.
CaCO3 precipitation depends mainly on the solubility product
value (Ks) which depends on the temperature. The Ks values of calcite
were calculated for different temperatures using the empirical
expression [26]:
pKs = 7:8156 + 0:031111T + 1502 = T  5:518: log T; ð6Þ
where “logT” is the logarithm of absolute temperature T (K).
They are respectively 10− 8.44, 10− 8.54 and 10− 8.67 at 20, 35 and
50 °C. Ks values show that when the temperature increases, CaCO3
solubility product decreases.
Fig. 2. Chronoamperometric curves obtained on gold electrode at 700 rpm in CCP water
of 30 °F hardness for different temperatures.
On the oxygen reduction plate, the reaction depends on dissolved
oxygen concentration, oxygen diffusion rate and diffusion layer
thickness. However, O2 flux density (NO2) at the electrode–solution
interface has the same value as the OH− flux density (NOH−). It has
been shown that the interfacial pH doesn't vary with the Reynolds
number (velocity of the RDE) [27]. On the other hand, for potential
average −1 V/SCE, H2 production according to the Eq. (2) must be
taken into account. H2 production reaction is active with the
temperature increase which leads to increasing of OH− amount. A
light increase of the local pH is awaited, and then CaCO3 precipitation
takes place. This phenomenon will be added to the influence of the Ks
variation with temperature.
To conclude, temperature considerably increases the scaling speed
and leads to shorter scaling times.
3.2. Optimisation of scale inhibitors content
The most effective concentrations of the five scale inhibitors used
were determined at 20 °C. The evolution of the current versus time
allows estimation of the inhibitor efficiency.
Polyphosphate compounds were added to CCP water (30 °F) at
different concentrations: HMPS (0.3 to 0.6 mg L− 1), STTP (0.1 to
0.6 mg L− 1) and MEDPHOS (65 to 90 µL L− 1). For these three
polyphosphates, this paper will focus principally on the results
obtained with the HMPS inhibitor.
Fig. 3 presents the evolution of the current density versus time in
CCP water (30 °F) containing HMPS (0.3, 0.4 and 0.6 mg L− 1). The
current values recorded in the presence of the inhibitor (curves 2–4)
start at an average of −0.38 mA cm− 2 and remain relatively stable
compared to that recorded in water without inhibitor (curve 1). The
low value of initial current recorded in the presence of inhibitor is
probably due to its adsorption on gold surface. This phenomenon was
observed with all inhibitors. According to Fig. 3, a concentration of
0.4 mg L− 1 HMPS or more seems sufficient to inhibit CaCO3
precipitation.
The effect of polycarboxylic acid was tested by adding RPI2000 at
concentrations varying from 1 to 6 mg L− 1. Fig. 4 presents the current
evolution versus time for CCP water (30 °F) with added RPI2000. In
the presence of the inhibitor, curves 2, 3, 4 and 5 do not follow the
same pattern as curve 1 and recorded currents are much more
important in time. In addition, the shape of the curve 2 is different
from those of curves 3, 4 and 5 which are similar among them.
Nevertheless, curve 3, obtained with adding 2 mg L− 1 of RPI2000,
presents higher current values. We explain the fall of the current
observed in the presence of a small quantity of inhibitor (curve 2) by
Fig. 3. Chronoamperometric curves obtained on gold electrode at 700 rpm in CCP water
of 30 °F hardness at 20 °C in the presence of HMPS for different concentrations.
 R. Ketrane et al. / Desalination 249 (2009) 1397–1404 1401

Fig. 4. Chronoamperometric curves obtained on gold electrode at 700 rpm in CCP water
of 30 °F hardness at 20 °C in the presence of RPI2000 for different concentrations.

the progressive covering of the electrode by the scale. At larger

inhibitor contents, the current increase indicates an activation of the
electrode following active sites release [22,28] necessary to the
reduction of O2 and H2 reactions.
In the presence of RPI2000, the concentration of 2 mg L− 1 or
higher appears to be adequate according to Fig. 4.
The polyphosphonate effect was tested by adding SECAL at various
concentrations (5, 15, 20 and 25 mL L− 1) in CCP water of 30 °F (Fig. 5).
Curves 2, 3, 4 and 5, obtained in the presence of SECAL, do not follow
the same pattern as curve 1, obtained without inhibitor. The currents
corresponding to curves 3, 4 and 5, are stable during the experiment.
Nevertheless, curve 3, corresponding to 15 mL L− 1 of SECAL, presents
higher current values. A concentration of 15 mL L− 1 or higher of
SECAL appears then to be the optimum concentration.

3.3. Temperature effect

The most effective concentrations of these five products to inhibit
scale formation were determined at 20 °C. They are in priori: 0.2 mg L− 1
of HMPS, 65 µL L− 1 of MEDPHOS, 0.4 mg L− 1 of STTP, 2 mg L− 1 of
RPI2000 and 15 mL L− 1 of SECAL. These concentration values were used
to study the temperature influence on inhibitors efficiency. For each
inhibitor added at its optimised concentration, tests were run in CCP
water (30 °F), for various temperatures from 20 °C until 50 °C. The
Fig. 6. Chronoamperometric curves obtained on gold electrode at 700 rpm in CCP water
of 30 °F hardness in the presence of the inhibitors for: (a) T = 20 °C and (b) T = 50 °C.
results are reported only for 20 and 50 °C (Fig. 6) because any notable
effect is observed for intermediate values. Now we compare the
effectiveness of the inhibitors added at their optimal concentration to
the CCP water for various temperatures.

Fig. 5. Chronoamperometric curves obtained on gold electrode at 700 rpm in CCP water Fig. 7. Chronoamperometric curves obtained on gold electrode at 700 rpm in CCP water
of 30 °F hardness at 20 °C in the presence of SECAL for different concentrations. of 30 °F hardness at 50 °C in the presence of HMPS for different concentrations.
1402 R. Ketrane et al. / Desalination 249 (2009) 1397–1404
Fig. 8. Chronoamperometric curves obtained on gold electrode at 700 rpm in CCP water
of 30 °F hardness at 50 °C in the presence of RPI2000 for different concentrations.
Fig. 9. Chronoamperometric curves obtained on gold electrode at 700 rpm in CCP water
of 30 °F hardness at 50 °C in the presence of SECAL for different concentrations.
At 20 °C (Fig. 6a), the scaling times obtained in the presence of
inhibitors in CCP water tend towards infinity (curves 2–6). The current
values remain relatively stable versus time (curves 2–6) compared to
Fig. 10. Scanning electron microphotograph (a) and energy dispersive spectrum (b) for scale obtained from CCP water of 30 °F hardness without inhibitor for 20 °C.
that obtained without inhibitors (curve 1). At this temperature all
inhibitors are efficient.
Fig. 6b presented the curves obtained in CCP water at 50 °C in the
presence of each inhibitor added at the optimal concentration which
is previously found at 20 °C. At t = 0 min, the current values with STTP
(curve 2), MEDPHOS (curve 4) and HMPS (curve 3) are respectively
−0.68, −0.74 and − 0.87 mA cm− 2. The current values in the pre-
sence of phosphates in CCP water (curves 2–4) start to drop in at the
beginning and the residual current recorded at 90 min is an average of
−0.25 mA cm− 2. Curve 5, obtained in the presence of RPI2000,
follows the same pattern. However, the residual current recorded
(average − 0.45 mA cm− 2) is higher than the one recorded with
phosphates. In the presence of SECAL, the curve obtained (curve 6)
has the same shape as curves 2–5. At the beginning, the current value
averages (−0.79 mA cm− 2) and starts to decrease after 30 min, the
current value is −0.45 mA cm− 2 at the end of the experiment.
The experimental tests showed that the inhibitors added to CCP
water at the optimal concentrations previously determined at 20 °C
are not effective at 50 °C (Fig. 6b). By increasing the inhibitor con-
centration, no improvement was recorded in the effectiveness of the
antiscalants at 50 °C (Figs. 7 and 8) except for the SECAL where the
concentration 20 mL L− 1 appears sufficient to inhibit the scale for-
mation as shown in Fig. 9.
To resume, the optimal concentrations obtained are: 0.2 mg L− 1 of
HMPS, 65 µL L− 1 of MEDPHOS, 0.4 mg L− 1 of STTP, 2 mg L− 1 of
RPI2000 and 20 mL L− 1 of SECAL but only the last one is effective at
50 °C. Moreover, the preliminary tests carried out with SECAL, via
polarization curves i = f(E), show a good electrochemical stability of
SECAL at the potential −1 V/SCE.
The experimental results obtained by chronoamperometry in the
presence of the five inhibitors added in CCP water (30 °F hardness) in
the range temperature 20–50 °C show that they act by threshold
effect. The optimised concentration value of scale preventer com-
pounds varies from one family of inhibitor to another.
Micrographies of the scale formed on the gold electrode were
taken using scanning electron microscopy. Shown in Fig. 10a is the
crystal electrodeposited for 90 min from CCP water (30 °F) without
any inhibitor at 20 °C. The formed crystals cover totally the electrode
area and present different allotropic forms. According to the EDS
analysis (Fig. 10b), the crystal layer is mainly constituted of calcium
which confirms the presence of CaCO3. The major regular structure
with defined cubic crystal characteristics corresponds to calcite [3].
This is confirmed by Raman spectroscopy observations focused on the
cubic particles (Fig. 11), the characteristic peaks of calcite were
detected (peaks at 284, 712 and 1085 cm− 1). Finally, it can be
concluded that CaCO3 is mainly present as calcite.
 R. Ketrane et al. / Desalination 249 (2009) 1397–1404
Fig. 11. Raman spectrum of scale obtained without inhibitors.
In the presence of SECAL inhibitor added to the CCP water at 20mL L− 1,
the SEM microphotograph obtained at 50 °C (Fig. 12a) shows essentially
the different depths of the mechanical polishing lines on the substrate
surface. Obviously, and in agreement with electrochemical results
(Fig. 9b), very few small particles of crystal are formed on the electrode
surface. EDS analysis (Fig. 12b) confirms the previous observations, as
no calcium was detected (only gold, work electrode constituent, is
detected). In the presence of SECAL, no scale was detected by Raman
spectroscopy on the electrode which confirms the inhibiting effect.
Calcium carbonate crystallization consists of two stages: nucle-
ation and growth. The adsorbed molecules of antiscalant are
presumed to inhibit scale formation by interfering with the two
processes involved in crystal formation.
Crystal growth takes place on the many small particles formed
during the nucleation stage [29]. This suggests that the inhibition
mechanism can be described by inhibitor adsorption on the earlier
particles formed during the nucleation stage, this will block the active
crystal growth sites [30]. The threshold effect of inhibitors also occurs
apparently by interfering with early crystal growth. In this case, the
effect is more pronounced with lower molecular weight molecules.
In the crystal growth stage, the inhibitor molecules retard the scale
growth when some inhibiting species are preferentially adsorbed on
active sites. Most inhibitor compounds possess large ions and are
presumed to require a relatively large crystal surface coverage for
Fig. 12. Scanning electron microphotograph (a) and energy dispersive spectrum (b) for scale obtained from CCP water of 30 °F hardness with SECAL for 50 °C.
1403
effective crystal growth retardation. After adsorption, scale deposit
structure can be significantly distorted and weakened.
All inhibitors were efficient at 20 °C. At high temperature (50 °C),
the results clearly show that polyphosphates, polyacrylic acid and
polyphosphonate scale preventers correctly inhibit at the beginning of
the experiment, but their efficiency drops with time. In the presence
of polyphosphonate, the current value recorded is higher than those
recorded in the presence of polyphosphate and polyacrylic acid. The
substance scale preventer which inhibits best at 50 °C is the SECAL at
20 mL L− 1. Concentration of 20 mL L− 1 seems higher, but notice that
SECAL is constituted of more than 50% of water.
At 50 °C, the phosphate inhibitors were shown to inhibit well
scaling at the beginning but end up losing their efficiency. This can be
explained by the fact that hydrolysis reaction of phosphates with
water is accelerated with rising temperature.
For polycarboxylates (RPI2000), the final current recorded at 50 °C
remains relatively high compared to phosphates. This means that
RPI2000 keeps only a part of its inhibiting capacity at this temperature,
as this compound adsorbs only on some crystal sites [18]. This ad-
sorption deteriorates the growth mechanism so that the crystals
develop slowly and are strongly deformed. Moreover, the structural
deformation of crystal involves a reduction in the adherence of the solid
thus formed. Then, this involves a delay of the crystal growth which
decreases the quantity of solid deposited on its surfaces.
In the case of phosphonates (SECAL), we noticed that the tem-
perature does not have any effect on the inhibiting efficiency of this
substance, even at the highest temperature (50 °C). Thus, SECAL
compound proves to be the best for the scaling inhibition considering
a large range of temperature. This result was more or less expected as
the phosphonates are usually used because they offer a better resistance
to hydrolysis than condensed phosphates at high temperatures.
4. Conclusion
The results obtained show that, to prevent scaling, the five com-
mercial inhibitors tested (HMPS, MEDPHOS, RPI2000, SECAL and
STTP) act by threshold effect. The optimal inhibition concentration
varies from one family of inhibitor to another. The five inhibitors
prevent CaCO3 from precipitation from 20 °C until 40 °C. Under our
experimental conditions, the obtained results showed that phospho-
nates are better inhibitors than polycarboxylates or polyphosphates.
Moreover, at 50 °C, most of the tested substances correctly inhibit at
the first moments but all end up losing their efficiency with time,
except for SECAL whose inhibiting capacity remained unchanged. This
1404 R. Ketrane et al. / Desalination 249 (2009) 1397–1404
inhibitor can be used for groundwater and geothermal water where
the water temperature can reach 50 °C.
Acknowledgement
This work was completed within the framework of Algerian-
french cooperation.
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