Desalination 375 (2015) 138148

Contents lists available at ScienceDirect

Desalination
journal homepage: www.elsevier.com/locate/desal

Performance of inhibitors on CaCO3 scale deposition in stainless steel &

copper pipe surface
Yousef M. Al-Roomi a,, Kaneez F. Hussain a, Mohammed Al-Rifaie b
a
b

Chemical Engineering Department, Kuwait University, P.O. Box 5969, 13060 Safat, Kuwait
Mechanical Engineering Department, Kuwait University, P.O. Box 5969, 13060 Safat, Kuwait

H I G H L I G H T S

G R A P H I C A L

A B S T R A C T

Low molecular weight maleic anhydride copolymers (YMR-polymers) as

scale inhibitors
Inhibitors were tested for CaCO3 scaling
at various temperatures.
Experiment was done in pipe ow system using steel and copper pipes.
Inhibition efciency up to 97.79% at
60 C and 92.74% at 70 C was observed.
SEM and XRD analysis show copolymer
changes morphology and size of CaCO3
crystals.

a r t i c l e

i n f o

Article history:
Received 24 March 2015
Received in revised form 29 July 2015
Accepted 30 July 2015

Keywords:
Maleic-anhydride
n-alkylacrylamide
CaCO3 scales
Inhibition efciency
Pipe ow system
SEM and XRD

a b s t r a c t
Novel low molecular weight copolymers (termed as YMR-series polymers) prepared through reaction of maleic
anhydride with n-alkylacrylamide monomers via nitroxide-mediated radical polymerization (NMRP), atom
transfer radical polymerization (ATRP) and free radical polymerization have shown feasibility as a new generation scale inhibitor. The scale inhibition property of these YMR-polymers towards CaCO3 in the articial cooling
water was studied in steel (316 L) and copper (90/10, CuNi alloy) pipes using a pipe ow system at various temperatures. The relationship between deposited scale mass and temperature was deduced from experimental
data. The effect on formation of CaCO3 scales was investigated with scanning electronic microscopy (SEM) and
X-ray powder diffraction (XRD) analysis. The results showed that the low molecular weight YMR-polymers
were excellent calcium carbonate scale inhibitor in copper and steel pipe ow system showing inhibition up to
98% at 60 C.
2015 Elsevier B.V. All rights reserved.

1. Introduction
Scaling is a difculty encountered in processing aqueous solutions
containing ions of sparingly soluble salts. Scale deposits can readily
form on ow surfaces when a solution is concentrated beyond the
Corresponding author.
E-mail address: yalroomi.kuniv@gmail.com (Y.M. Al-Roomi).

http://dx.doi.org/10.1016/j.desal.2015.07.028
0011-9164/ 2015 Elsevier B.V. All rights reserved.

solubility limit of a dissolved sparingly soluble salt or when a solution

containing an inverse solubility salt is in contact with a hot surface.
Such conditions are met in both thermal and membrane desalination
processes [1,2].
This paper continues our research efforts in the discovery, design
and application of novel maleic anhydride based polymers (termed
YMR-series polymers) as scale inhibitors. Results obtained from our
previous communication [3] for YMR-series polymers have shown

Y.M. Al-Roomi et al. / Desalination 375 (2015) 138148

feasibility as a new generation scale inhibitor for CaSO4 scales. Hence

pursuance of these polymers with other mineral scales is a requisite in
the nal endeavor to utilize in industry. One of the most common mineral scales is CaCO3 which is the subject of this paper. The formation of
calcium carbonate is not only a common crystallization phenomenon
that forms in natural processes (e.g. biomineralization), but represents
a fouling problem known as scaling, which is present in various industrial processes and technologies [46]. Scale deposition cannot be tolerated because of its highly deleterious effects on production capacity and
specic energy consumption.
To mitigate the problem of mineral scaling, chemicals and
antiscalants are commonly used. The antiscalant technique is cost effective: in many cases scaling can be suppressed with less than 10 mg/L of
the antiscalant due to physical mechanisms rather than chemical mechanisms [7]. Some functionalities of antiscalants are: (1) At the submicroscopic level of crystallization, negatively charged groups located on the
antiscalant molecule target the positive charges on scale nuclei and distort the ionic balance that propagates crystal growth. (2) Antiscalants
will adsorb to the crystal forming constituents and repel other ions,
keeping them in solution, preventing particles from xing to anionic
charges present on the membrane surface. (3) Sub-stoichiometric
amounts of antiscalants prevent the precipitation of salts once the salt
has exceeded its solubility product, called threshold inhibition. (4) At
equimolar amounts of antiscalants and scale forming ions, antiscalants
may act as a chelating agent. Antiscalants form soluble complex molecules with particular metal ions, inactivating the ions so that they cannot react with other elements or ions to produce precipitates or scale
[8]. Commonly used antiscalants include condensed polyphosphates,
organophosphonates, and polyelectrolytes. Effective polyelectrolyte
inhibitors are mostly polycarboxylic acids, e.g., polyacrylic acid,
polymethacrylic acid and polymaleic acid.
Polyphosphonate inhibitors easily lead to the formation of orthophosphate because of their own hydrolysis or decomposition and orthophosphate itself can react with calcium ions to form relatively insoluble
calcium phosphate scale [9]. High levels of phosphonates are becoming
increasingly restricted in terms of release to the environment. As a
result phosphorous free and less toxic scale inhibitors such as
polyacrylates and derivatives of polycarboxylic acid and various maleic
and sulfonic acid homo- and co-polymers are gaining importance
[1013]. Anti-scalants based on polycarboxylic acid also have the additional advantage of having dispersion properties with regard to calcium
carbonate. Polymers with negatively charged groups can adsorb onto
the surfaces of crystals and particles in suspension and impart a like
charge, hence repelling neighboring particles, thereby preventing agglomeration and keeping the particles suspended in solution [14,15].
However the antiscalant performance of polycarboxylate is dependent on the number of carboxyl groups, spatial arrangement of the functional group and molecular weight. Polyacrylates with molecular
weight in the range of 5006000 are the most widely used due to
their high scale inhibition power and environmental compatibility
[1618]. Polymers are generally of low molecular weight to prevent
bridging of suspended solids, but of sufcient structure to adhere to developed scale formation i.e. they can be adsorbed onto the active growth
sites of the crystal surface, and disturb the regular outgrowth of CaCO3
crystal [19].
This work forms part of ongoing research projects aiming to synthesize and characterize novel low molecular weight maleic-anhydridenalkylacrylamide copolymers (YMR-series polymers) and to provide
an objective assessment of the effectiveness of these YMR-series
antiscalants, on the suppression of calcium carbonate scales. These
low molecular weight maleic anhydride based polymers were synthesized by us via free radical polymerization [20,21], atom transfer radical
polymerization (ATRP) [22] and nitroxide mediated radical polymerization (NMRP) mechanism [23]. The performance of these polymers as an
antiscalants for the inhibition of CaCO3 precipitation was studied
through static scale inhibition test [24].

139

1.1. Objective of this study

In order to develop effective antiscalant on industrial level it is
necessary to clarify whether maleic anhydride based copolymers
(termed YMR-series polymers) are good scale inhibitors for calcium
scale growth. In this study we rst examined the effectiveness of the
polymers on CaCO3 scales at different dosage level of the antiscalant
(as per the standard NACE TM 0374-95 and ASTM D 1126-02). Based
on the scale inhibition efciency, polymers showing highest scale inhibition efciency were selected and investigated in suppressing CaCO3
scale deposition in steel (316 L) and copper (90/10, CuNi alloy) pipes
using a pipe ow system. As the next step ve best performing
antiscalants were chosen and tried at various temperatures. Finally a
comparative study of scaling rate at different temperatures with time
for best performing antiscalant in steel and copper pipe ow system is
carried out. The morphologies and crystal structures of precipitates
were investigated using scanning electron microscope and X-ray
powder diffraction analysis.
2. Experimental
2.1. Synthesis and experiments
All these YMR-series polymers which were evaluated for scale
inhibition property towards CaCO3 scales are depicted in Table 1. The
brief synthesis of these polymers is given below:
2.1.1. General monomer synthesis
Substituted amine (n-alkyl amines/benzamide) and barium hydroxide (w/w; 1%) were placed in the 200 ml round bottom ask placed in
an ice bath. Acrolyl chloride was added with continuous stirring till
the reaction mixture thickened. The reaction mixture was then heated gradually up to 85 C, until hydrogen chloride was eliminated. The
resulting solution was whitish-yellow and turbid. Doubly deionized
water or water CHCl 3 mixture (1:3) was added to the vessel with
vigorous stirring to separate the monomer. Similarly ve different
monomers i.e. N-Octylacrylamide (AAO), N-Propylacrylamide
(AAP), N-Butylacrylamide (AAB), N-Hexylacrylamide (AAH) and NAcryloylbenzamide (ABA) were synthesized [2024].
2.1.2. Free radical polymerization
All homo-polymerization studies were conducted with 0.0617 mol
monomer maleic anhydride in 250 ml of solvent O-Xylene or Toluene
under N2 atm at temperatures 110 C and 143 C [20,21]. Two different
initiators Azo-isobutyronitrile (AIBN) and Benzoyl peroxide (BPO)
at concentration of (5, 7.5, 10, 12 and 15 mol% of monomer) were
used for homopolymerization.
Copolymerization of MA with AAO was conducted at four different
concentrations [20,21]. The samples were labeled as: MA/30 AAO, MA/
50 AAO, MA/60 AAO and MA/40 AAO indicating 70:30, 50:50, 40:60
and 60:40 mol% of MA:AAO, respectively. Two different initiators azoisobutyronitrile (AIBN) and benzoyl peroxide (BPO) at varying concentrations (5, 7.5, 10 and 12 mol% of monomers) were used in the copolymerization study.
2.1.3. Copolymerization by ATRP
Copolymerization of MA with n-alkylacrylamide monomers was
conducted at 5:5 monomer ratios in o-xylene using a FeCl2/SA catalyst
system initiated by 2-chloropropionitrile (CPN) or methyl-2-chloropropionate (MCPN) [22]. The contents were purged with N2 to eliminate O2 for approximately 15 min. The reaction was conducted at
three different molar ratios of [monomers]/[initiator]/[FeCl2]/[SA], i.e.
(100:1:1:1), (100:1:1:2) and (100:1:1:4) respectively. The temperature
of the reaction was maintained at 140 C.

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Y.M. Al-Roomi et al. / Desalination 375 (2015) 138148

Table 1
Conditions and results for the polymerization of YMR-series polymers in o-xylene at 140 C.
Monomers
(Mol %)

Initiator
(Mol %)

Mn GPC

YMR47

MAa

BPOb (10)

847

YMR40

MA

BPO (5)

641

YMR34

MA

AIBNc (15)

457

Antiscalant

MA

YMR44

AIBN ( )

400

AIBN (7.5)

1890

AAO (50)

BPO (7.5)

1759

AAO (50)

AIBN (10)

1725

MA (50)

AAO (50)

BPO (10)

1364

YMR82

MA (60)

AAO (40)

BPO (7.5)

1345

YMR83

MA (50)

AAO (50)

AIBN (12)

1267
1466

YMR74

MA (50)

AAOd (50)

YMR68

MA (50)

YMR63

MA (50)

YMR76

YMR 142A

MA (50)

AAHe (50)

CPNf /FeCl2 /SAg

(1:1:4)

YMR 154A

MA (50)

AAH (50)

MCPNh /FeCl2 /SA

(1:1:4)

1280

YMR 144A

MA (50)

AAB (50)

CPN /FeCl2 /SA

(1:1:4)

1215

YMR 152A

MA (50)

AABi (50)

MCPN /FeCl2 /SA

(1:1:4)

1020

YMR 151A

MA (50)

AAB (50)

MCPN /FeCl2 /SA

(1:1:4)

859

AAP (50)

CPN /FeCl2 /SA

(1:1:1)

610

YMR 146A

MA (50)

Reaction

Free radical
homopolymerization

Free radical
copolymerization

YMR 131S
YMR 133S
YMR 134S
YMR 121S
YMR 136S
a

MA (50)
MA (50)
MA (50)
MA (50)
MA (50)
MA (50)

AAB (50)

BPO / TEMPO
(10:10)

1116

AAPk (50)

BPO / TEMPO
(3:7)

888

AAH (50)

BPO / TEMPO
(10:5)

813

AAH (50)

BPO / TEMPO
(10:10)

680

ABAl (50)

BPO / TEMPO
(5:15)

560

AAP (50)

BPO / TEMPO
(10:5)

537

2.2. Evaluation of the antiscalants

2.2.1. Anti-precipitation test
All the chemicals were reagent grade and the brines were prepared
as per the standard NACE TM 0374-95. Tests were conducted as per the
standard NACE TM 0374-95 and ASTM D 1126-02.

Atom transfer
radical
polymerization

YMR 135S

2.1.4. Copolymerization by NMRP

Copolymerization of MA with n-acrylamide monomers was conducted at 5:5 monomer ratios in o-xylene [23]. The contents were
purged with N2 to eliminate O2 for approximately 15 min. The reaction
was conducted at ve different concentrations of 2,2,6,6-tetramethyl-1piperidinyloxy (TEMPO) and BPO, i.e. (TEMPO: BPO 10:5), (TEMPO:
BPO 7:3), (TEMPO: BPO 10:10), (TEMPO: BPO 5:10), (TEMPO: BPO
15:5) mole % of monomer, respectively.

Nitroxide mediated
radical
polymerization

Maleic anhydride monomer (MA). Benzoyl Per Oxide (BPO). cAzoisobutyronitrile

(AIBN). dN-Octylacrylamide monomer (AAO). eN-Hexylacrylamide monomer (AAH). f2chloropropionitrile (CPN). gSuccinic Acid(SA). hMethyl-2-chloro-propionate (MCPN). iNButylacrylamide monomer (AAB). j2,2,6,6-tetramethyl-1-piperidinyloxy (TEMPO). kNPropylacrylamide monomer (AAP). lN-Acryloyl benzamide monomer (ABA).

2.2.2. Pipe ow system

The pipe ow system consisted of equimolar solution of calcium
chloride and sodium bicarbonate in predetermined concentrations that
were placed in a water bath until they reached the required temperature. The vessels were purged with CO2 gas at a rate of 250 ml/min
for 20 min, by bubbling CO2 through a fritted-glass gas dispersion
tube immersed to the bottom of the container. The solutions were
transported through the test section at the same ow rate by using a
double line peristaltic pump (Fig. 1). The two solutions were mixed at
the inlet of the test section, which consisted of 1/8 OD, 0.028 wallthickness, 4 long, steel pipe loop (316 L; ASTM-A269) or 1/8 OD,
0.030 wall-thickness, 4 long, copper pipe loop (90/10, CuNi alloy;
ASTM-B111). These sample pipe loops serving as scaling surface were
placed in a circulating water bath with heating unit to control temperature. The inlet and outlet of these pipe loops were connected with pressure data logger to measure the pressure difference in the pipe sample
arising due to scale accumulation. The pressure data loggers were in
turn connected to the computer and pressure data's were automatically
measured within set time interval.
After a set time the data from the pressure data logger was
downloaded in the computer, pump was switched off and the test section detached. The copper or steel pipe samples were withdrawn out

Fig. 1. Diagram for pipe ow system.

Y.M. Al-Roomi et al. / Desalination 375 (2015) 138148

141

of the units and placed in an oven at 50 C overnight, then cooled down

to room temperature and weighed. The mass of scale deposit was the
difference between the weight of the pipe samples before and after
the experiments. These experiments were performed for 0.15 M solution of CaCO3, blank and with various antiscalants at 0.5 ppm concentrations and different temperatures keeping the ow rate constant at 1
ml/min, so as to investigate the effect of varying antiscalants.
2.3. Scanning electron microscope (SEM) studies
The shape and morphological changes of the calcium carbonate crystals upon addition of the antiscalants were examined using JEOL 6300
unit. SEM observations were made after gold sputtering.
2.4. X-ray powder diffraction (XRD) analysis
The CaCO3 crystals were also characterized by XRD analysis. XRD
patterns were obtained using SIEMENS D5000 X-ray diffractometer
equipped with a position sensitive detector. The powder (XRD) patterns
were collected in angular range between 10 and 80 at 2, with a 2
scan step of 0.015 and step time of 0.2 s, using CuK1 radiation ( =
1.5406 Ao) and Ni lter. The computer program DIFFRACplus (Bruker
AXS, Inc., 2004) with ICDD library was used to identify the minerals.
3. Result and discussion
3.1. Effect of dosage on the efciency of scale inhibition
All the YMR-series antiscalants synthesized by us [2024] were tested with several repeating runs for their efciency of scale inhibition at
varying inhibitor dosages in the range from 0.1 to 5 ppm level (Fig. 2).
Tests were conducted as per the standard NACE TM 037495 and
ASTM D 112602. Percentage inhibition was calculated by using equation below:
% inhibition

 2 


Ca antiscalant Ca2 blank
x100
Ca2 original Ca2 blank

where [Ca2+]antiscalant is concentration of Ca2+ ions in the ltrate in the

presence of antiscalant after CaCO3 supersaturated solutions were
heated for 24 h at 70 C and 10.45 pH, [Ca2+]blank is the concentration
of Ca2+ ions in the ltrate in the absence of inhibitor after CaCO3 supersaturated solutions were heated for 24 h at 70 C and 10.45 pH and
[Ca2+]original is concentration of Ca2+ ions at the beginning of the experiment. From Fig. 2 it can be seen that the efciency of scale inhibition increases evidently with the increasing inhibitor dosage. However, when
dosage reaches threshold, the efciency of scale inhibition increases
little with increasing inhibitor dosage as can be seen in Fig. 2(c).
3.2. Evaluation of the antiscalants in pipe ow system
All the YMR-series antiscalants showed scale inhibition effect in the
range of 3095% for CaCO3 [2024], based on this criterion antiscalants
showing higher scale inhibition efciency were selected at 0.5 ppm concentration and the same concentration was xed for all our experiments
of the pipe ow system. All these YMR-series polymers which were
evaluated for scale inhibition property towards CaCO3 scales for pipe
ow system are depicted in Table 1.
A 0.15 M CaCO3 solution containing antiscalant (0.5 ppm) passes
through the sample pipe loops serving as scaling surface. The inlet and
outlet of these pipe loops were connected with pressure data logger to
measure the pressure difference in the pipe sample arising due to
scale accumulation, which in turn was connected to the computer and
pressure data's were automatically measured within set time interval.
The pressure difference in sample pipes arising due to scale accumulation with time (20 min.) is observed in Fig. 3. It's observed that as the

Fig. 2. Variation of inhibition efciency versus dosage of inhibitors for different YMRseriers polymers.

CaCO3 scale inhibition efciency of the antiscalant increases the pressure drop decreases. In other words for antiscalants showing better
scale inhibition efciency, there was very little CaCO3 scale deposit in

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Y.M. Al-Roomi et al. / Desalination 375 (2015) 138148

Fig. 3. Effect of scale accumulation on pressure in the pipe with time (20 min.) in blank and different antiscalants in copper and steel pipe ow system for 0.15 M CaCO3 solution at 0.5 ppm
antiscalant concentration.

the sample pipe and hence a very low pressure drop of 0.007 psi was observed as compared to pipe sample containing blank solution (without
scale inhibitor) where the scaling was very high and hence the pressure
drop increased to 0.099 psi for copper pipe and 0.089 psi for steel pipe.
Based on these ve best performing antiscalants (YMR 142-A, YMR-74,
YMR-63, YMR 154-A and YMR 135-S) were selected and tried at various
temperatures.

3.3. Effect of temperature on scale inhibition

The effect of temperature on the scale inhibition with different
antiscalnts at 0.5 ppm concentration in copper and steel pipes is
shown in Fig. 4. Maximum inhibition in the range 9298% is observed
at 60 C. Generally, within the investigated temperature range 60
75 C, the higher the temperature, lesser the inhibition. For a 0.15 M
solution of CaCO3 the amount of scale tripled and hence the inhibition
decreased when the temperature was increased from 60 C to 70 C
for both copper and steel pipe system as can be observed from the
graphs. But a further small rise in temperature from 70 C to 75 C almost decreased the inhibition 3 times which shows that with increase
in temperature from 60 C to 70 C there is a 611% decrease in inhibition efciency whereas further 5 C temperature increase, decreases the
inhibition efciency up to 58%. This can also be observed from the scale
formation for the blank and with antiscalants at 0.5 ppm concentration
in copper and steel pipes as shown in Table 2. One of the reasons for this
could be inverse solubility of CaCO3 in water as the temperature increases, [25,26]. Another reason for this behavior could be that higher
temperature provides enough energy to the molecules to overcome
the activation energy of the precipitation reaction and sped up the
transport of scale components from bulk solution to the surface [27].

3.4. Relation between scaling rate and temperature

Based on the inhibition efciency in foregoing discussion we observe
that YMR-74 shows best inhibition effect and rate of scale formation in
its presence is much lower as compared to other antiscalnts. Therefore
Table 2
Effect of Temperature on Scale Mass (103 kg/m2) for different pipe systems, in 0.15 M
CaCO3 solution at 0.5 ppm antiscalant concentration for 20 min.

Fig. 4. Effect of inhibition percent with temperature on scale formation for copper and
steel pipe ow system, run time = 20 min for 0.15 M CaCO3 solution at 0.5 ppm
antiscalant concentration.

Temperature
(0C)

BLANK

60

0.0627

0.0015

0.0055

0.0062

0.0041

0.0037

65

0.0701

0.0031

0.0081

0.0089

0.0062

0.0051

70

0.0771

0.0056

0.011

0.0117

0.0095

0.0076

75

0.0849

0.0106

0.0149

0.0156

0.0128

0.012

60

0.0589

0.0013

0.0043

0.005

0.0039

0.004

65

0.0621

0.0029

0.0067

0.0085

0.0065

0.006

70

0.07

0.01

0.01

0.0157

0.0099

0.01

75

0.07

0.01

0.02

0.026

0.017

0.01

YMR74

YMR 154A YMR 135S YMR 142A YMR63

Y.M. Al-Roomi et al. / Desalination 375 (2015) 138148

143

12 106 kg/m2 in just 6 min. The scales were formed so abundantly

that it started blocking the ow after 6 min at 75 C. Similar results
were obtained for steel pipe (Fig. 6) where the scale mass increased
from 8 106 kg/m2 at 60 C to 1 10 5 kg/m2 at 75 C in just
6 min. To obtain the values of average scaling rate, the scale amount
deposited was divided by time. Plotting average scaling rate against
run time produces a straight line (Fig. 7) with a slope k as indicated in
Eq. below [27]:
1 dm
kt C
Ar dt

where,
dm/dt
Ar
T
C
k

the scaling rate (kg/min)

the total scaling area of the pipe (m2)
run time (min)
constant
constant, referring to the change rate of the scaling rate
(/m2 min).

The k constant derived from the curves in Fig. 7 are listed in graph.
It shows that as the temperature rises rate constant also increases,
showing a signicant increase from 70 C to 75 C.
Fig. 5. Plot of scale amounts against time at various temperatures for YMR-74 (0.5 ppm) in
copper pipe ow system for 0.15 M CaCO3 solution.

YMR-74 was further investigated at different time with varying temperature in 0.15 M CaCO3 solution at 0.5 ppm antiscalant concentration for
copper and steel pipe. To determine the correlation between scaling
rate and temperature the amount of calcium carbonate at different temperatures is plotted against time (Figs. 5 & 6). The plot show that the
curves are parabolic indicating scale amount is quadratic function of
run time. For copper pipe (Fig. 5) it is observed that temperature
seemed to signicantly promote the scaling of CaCO3. The scale mass
was 9 106 kg/m2 at 60 C in 20 min time but as the temperature increased to 75 C the rate of scale formation also increased and reached

Fig. 6. Plot of scale amounts against time at various temperatures for YMR-74 (0.5 ppm) in
steel pipe ow system for 0.15 M CaCO3 solution.

3.5. Scanning electron microscope studies

In order to investigate the effect of scale inhibitor on the growth and
morphology changes of CaCO3 crystals, the CaCO3 scales formed in the
absence and presence of YMR-polymers were characterized by SEM
analysis. The SEM photographs for the CaCO3 with and without the

Fig. 7. Comparison of scaling rate at different temperatures for YMR-74 (0.5 ppm) in
(a) copper pipe ow and (b) steel pipe ow system for 0.15 M CaCO3 solution.

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Y.M. Al-Roomi et al. / Desalination 375 (2015) 138148

presence of the polymer are presented in Figs. 811. The crystal habit of
calcium carbonate has at least three forms: calcite, aragonite and
vaterite, depending on the temperature. The vaterite crystals are usually
formed at low temperature. The aragonite crystals are needle [28] and
ower like structures [29] while the calcite crystals are block like [28]
particles of cubic shape [29] or entangled rhombohedra [30]. In the
present study, crystals of calcite are formed in the absence of scale inhibitor which can be observed in Figs. 811 and also it's conrmed by
our previous publication [2224]. We have studied the effect of YMR
polymers on the calcite crystals and found that there is an alteration

Fig. 8. SEM images of CaCO3 scale deposited on steel pipe walls for Blank solution. From
top: (a) Blank (20 min; 60 C); (b) Blank (12 min; 65 C); (c) Blank (6 min; 75 C).

in crystal size. The SEM micrographs in presence of scale inhibitor reveal

that the scale deposit consists mainly of distorted calcite crystals with
rough rounded edges fused together and also sludge like precipitates.
There is a total disappearance of cubic shape, block like structures of
calcite crystals.
From Fig. 8(ac) for steel pipes its observed that at temperature
60 C, 65 C and 75 C for blank (without any inhibitors) the scale deposition is very high and almost complete blockage can be observed within

Fig. 9. SEM images of CaCO3 scale deposited on steel pipe walls for YMR-74 (0.5 ppm).
From top: (a) YMR-74 (20 min; 60 C); (b) YMR-74 (12 min; 65 C); (c) YMR-74
(6 min; 75 C).

Y.M. Al-Roomi et al. / Desalination 375 (2015) 138148

145

Fig. 10. SEM images of CaCO3 scale deposited on copper pipe walls for Blank solution. From
top: (a) Blank (20 min; 60 C); (b) Blank (12 min; 65 C); (c) Blank (6 min; 75 C).

Fig. 11. SEM images of CaCO3 scale deposited on copper pipe walls for YMR-74 (0.5 ppm).
From top: (a) YMR-74 (20 min; 60 C); (b) YMR-74 (12 min; 65 C); (c) YMR-74 (6 min;
75 C).

20 min. for 60 C, 12 min for 65 C and 6 min for 75 C, and long needle
shaped structures are formed but as the temperature rises from 60 C to
75 C there is an absence of tubular structure and at 70 C we observe
spongy deposit. Although at lower temperature of 65 C scales contain
only aragonite crystals but at higher temperature of 75 C other forms
of CaCO3 crystals may exist (conrmed by XRD analysis) which leads
to very fast scale deposition, causing the blockage of the ow in the
test unit.
Fig. 9(ac) shows the deposition of CaCO3 scales in the presence of
antiscalant YMR-74. There is almost no scale deposition within

20 min. for 60 C, 12 min for 65 C and although a small deposition is observed in 6 min at 75 C. This lack of scale deposition shows the efciency of YMR-74 as scale inhibitor as compared to the blank which shows
blockage within the same range of time.
Similar results are observed for copper pipes also for blank and in
presence of YMR-74 antiscalant at 60 C, 65 C and 75 C at different
time shown in Figs. 1011. In blank complete blockage is observed
and almost no scaling takes place in presence of antiscalant YMR-74 at
60 C and 65 C with varying time (Fig. 11). But as the temperature
increases to 75 C slight scaling is observed.

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Y.M. Al-Roomi et al. / Desalination 375 (2015) 138148

3.6. X-ray powder diffraction (XRD) analysis

The CaCO3 crystals were also characterized by XRD analysis. The
computer program DIFFRACplus (Bruker AXS, Inc., 2004) with ICDD
library was used to identify the minerals. Figs. 12 and 13 presents the
XRD images of CaCO3 crystals in the absence and presence of YMRpolymer. As shown in Fig. 12(a) in the absence of scale inhibitor
(YMR-polymer) at 65 C, the diffraction peak at 29.452 was the strongest peak which corresponds to the calcite crystal phase 104. In addition
other diffraction peaks at 23.069, 31.547, 35.966, 39.429, 43.164,
47.146, 47.646, 48.580, 56.559, 57.401, 60.693 and 64.654 corresponds to the calcite crystal faces 012, 006, 110, 113, 202, 024, 018,
116, 211, 122, 214 and 300 were observed respectively. This indicated
that calcite was the main crystal formed in the absence of scale inhibitor.
In the presence of scale inhibitor at 65 C as shown in Fig. 12(b), the
diffraction peaks of calcite as observed in Fig. 12(a) had completely disappeared except the peak at 29.452, 43.164 and 47.646 which were
greatly reduced and almost invisible. Instead the diffraction peaks of

aragonite are seen at 26.180, 27.140, 31.040, 33.060, 36.040,

37.820, 38.520, 42.840, 45.761, 48.320, 50.199, 52.400 and
52.940 which corresponds to 111, 021, 002, 012, 200, 031, 112, 220,
221, 202, 132, 113 and 231 crystal faces. In addition much reduced diffraction peaks of vaterite phase at 32.778, 38.818 and 39.456 are also
visible which corresponds to crystal faces 114, 211 and 205.
Fig. 13 represents the XRD images of CaCO3 crystals in the absence
and presence of YMR-polymer at 75 C. In absence of scale inhibitor
the main peaks are from calcite crystals at 23.022, 29.406, 35.966,
39.402, 43.146, 47.124, 47.490, 48.514, 56.555 and 57.402 corresponds to the calcite crystal faces 012, 104, 110, 113, 202, 024, 018,
116, 211 and 122 indicating that calcite was the main crystal formed
in the absence of scale inhibitor indicated in Fig. 13(a). In presence of
scale inhibitor (Fig. 13(b)) along with the calcite phase vaterite phase
is also observed at 21.005, 24.900, 27.048, 32.778, 39.456, 43.849,
50.079 and 62.870 corresponds to vaterite crystal faces 004, 110,
112, 114, 205, 300, 118 and 308 respectively. There are no peaks
corresponding to aragonite conrming its absence. From the

Fig. 12. XRD patterns of the CaCO3 crystals at 65 C in the absence of scale inhibitor (a), in the presence of scale inhibitor (b). A: aragonite; V: vaterite; C: calcite.

Y.M. Al-Roomi et al. / Desalination 375 (2015) 138148

147

Fig. 13. XRD patterns of the CaCO3 crystals at 75 C in the absence of scale inhibitor (a), in the presence of scale inhibitor (b). V: vaterite; C: calcite.

Fig. 13(b) it's obvious that in presence of scale inhibitor at 75 C temperature the intensity of the characteristic peak for calcite at 29.406
corresponding to crystal face 104 is greatly reduced.
This indicates that calcite is the dominant crystal formed in the absence of scale inhibitor (Figs. 12(a) & 13(a)). In the presence of scale inhibitor, the dominant crystal formed is aragonite and vaterite, and the
diffraction peaks of calcite are greatly reduced or almost invisible
(Figs. 12(b) & 13(b)). In other words the scale inhibitor delays the transformation from the less stable vaterite and aragonite phase, into the
most stable calcite phase. Whereas in the absence of scale inhibitor
the less stable aragonite and vaterite phases have managed to transform
into more stable calcite phase.
Calcite is the most thermodynamically stable and vaterite is the least
stable form in the three polymorphic forms of CaCO3 [2830]. In the absence of scale inhibitors calcite can be formed from the transformation
of aragonite or vaterite [31,32]. Vaterite is the initial phase formed in
many CaCO3 supersaturated solutions and then gradually transforms
to calcite [33]. Although calcite has the greatest thermodynamic stability under ambient conditions, however in the presence of scale

inhibitors, the thermodynamically less stable aragonite and/or vaterite

phases may be stabilized. It was found that thermodynamically unstable
aragonite and vaterite phases could be stabilized kinetically in the presence of YMR-polymer.
4. Conclusion
YMR polymers have shown excellent inhibition efciency for 0.15 M
CaCO3 solution at 0.5 ppm level. Inhibition efciency up to 97.79% at
60 C, 92.74% at 70 C but as the temperature increases to 75 C there
is 610% decrease in efciency. Therefore solution temperature proved
to have important effects on scaling. Higher temperature speeds up scaling process. Besides if the dosage level is increased to 1 ppm level complete inhibition could be observed at higher temperatures. Scanning
electron microscopy (SEM) and X-ray diffraction (XRD) analysis
showed that the YMR-polymers had great impact on the growth rate
and morphology of CaCO3 crystal. SEM images and XRD pattern indicate
that the polymers altered the morphology and size of calcium carbonate
crystals. In the presence of YMR-polymer at 65 C, the highly dispersed

148

Y.M. Al-Roomi et al. / Desalination 375 (2015) 138148

and unstable aragonite phase became the main crystal form in CaCO3
scale. At higher temperature of 75 C the polymers could disturb the
calcite growth and induce vaterite growth. These polymers can be safely
used up to a temperature of 75 C and up to pH 10.45 at a very low
dosage level of 0.5 ppm.
Acknowledgment
The authors wish to acknowledge Research Administration Department of Kuwait University for having provided the necessary funds
from Project RE05/06 for carrying the research work.
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