Desalination 340 (2014) 110

Contents lists available at ScienceDirect

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

Synthesis of uorescent-tagged scale inhibitor and evaluation of its

calcium carbonate precipitation performance
Huchuan Wang a, Yuming Zhou a,b,, Qingzhao Yao a,b, Shuaishuai Ma a, Wendao Wu c, Wei Sun c
a
b
c

School of Chemistry and Chemical Engineering, Southeast University, Nanjing 211189, China
Jiangsu Optoelectronic Functional Materials and Engineering Laboratory, Southeast University, Nanjing 211189, China
Jianghai Environmental Protection Co., Ltd, Changzhou 213116, Jiangsu, China

H I G H L I G H T S

Preparation of water soluble copolymer scale inhibitor

Characterizations of FT-IR and 1H NMR methods
The inhibition efciency to calcium carbonate scale
Could be used in the system of the high hardness water and accurate to determine concentration
Scale inhibition mechanism

a r t i c l e

i n f o

Article history:
Received 21 November 2013
Received in revised form 27 January 2014
Accepted 15 February 2014
Available online 7 March 2014
Keywords:
Fluorescent-tagged
Copolymer
Calcium carbonate
Scale inhibitor
Cooling water systems

a b s t r a c t
A novel uorescent-tagged scale inhibitor, maleic anhydrideoxalic acidallypolyethoxy carboxylate8-hydroxy1,3,6-pyrene trisulfonic acid trisodium salt (pyranine) (MAAPEMAPTA) was synthesized by maleic anhydride
(MA), oxalic acidallypolyethoxy carboxylate (APEM) and 8-hydroxy-1,3,6-pyrene trisulfonic acid trisodium salt
(APTA). Structures of APTA, APEM, and MAAPEMAPTA were carried out by FT-IR and 1H NMR. The observation
shows that the dosage of MAAPEMAPTA plays an important role on CaCO3 inhibition. It can be concluded that
the order of preventing the precipitation from ask tests was MAAPEM N MAAPEMAPTA N T225 N PESA N PAA HPMA. Relationship between MAAPEMAPTA's uorescent intensity and its dosage was
studied. Correlation coefcient R2 of MAAPEMAPTA's is 0.9973. The effect on formation of CaCO3 was investigated with combination of scanning electronic microscopy (SEM), transmission electron microscope (TEM), X-ray
powder diffraction (XRD) and FT-IR analysis. MAAPEMAPTA can be used to accurately measure copolymer consumption on line besides providing excellent CaCO3.
2014 Elsevier B.V. All rights reserved.

1. Introduction
In recent years, a common problem in circulating cooling water system is scale deposition. The commonly occurring scales are calcium carbonate, calcium sulfate, magnesium hydroxide, barium sulfate, calcium
phosphate, calcium oxalate, etc., among which calcium carbonate is
considered the most frequent. Scale can consist of one or more mineral
combination [13]. When scale problems occur on the surface of the facilities, it could cause a total or partial obstruction of pipes and decrease
the heat transfer, and even make the boiler burst [47]. The most common and effective method of scale controlling is the use of chemical additives as scale inhibitors that retard or prevent scale formation even in
very small concentrations [8,9]. There are many classes of chemicals
Corresponding author at: School of Chemistry and Chemical Engineering, Southeast
University, Nanjing 211189, China. Tel.: +86 25 52090617.
E-mail address: ymzhou@seu.edu.cn (Y. Zhou).

http://dx.doi.org/10.1016/j.desal.2014.02.015
0011-9164/ 2014 Elsevier B.V. All rights reserved.

used as scale inhibitors to prevent scale formation. These are watersoluble molecules or polymers with several functional groups, the
most common groups being phosphonate, carboxylate and sulfonate.
Although the phosphonate and sulfonate containing scale inhibitor are highly efcient as a scale inhibitor, their use is being restricted due to environmental legislation, which restricts their application
in cooling water system. In addition, phosphonates, when reverted
to orthophosphates, are potential nutrients for algae [10]. As a result,
the current trend for inhibitors' use is towards more environmentalfriendly green chemicals that are undoubtedly the trend of development [11,12]. Recently, Kessler reported a novel nonphosphorus
scale inhibitor. It is acrylic acid (AA)ammonium allylpolyethoxy
sulfate (APES) copolymer [1315]. However, it is quite difcult to
test for AAAPES by the traditional way because there is no phosphate
active component in it. Improper feed rate of treating agent leads to
serious problems. Another defect of AAAPES is that it still contains
nitrogen nutrition.

H. Wang et al. / Desalination 340 (2014) 110

Fig. 1. Preparation of APEM.

For the concentration determination several analytical methods

such as turbidimetric, potentiometric, uorescent tracer and spectrometric methods are available [16]. Fluorescence methods provide direct
measurement and control of a wide array of treatment actives [1719].
Presently, there are two methods to prepare uorescent polymers. One
is the copolymerization of a monomer containing a uorescent chromophore and other monomers, the other is chemical modication of polymers by uorescent groups [20,21]. There exist some reports about the
uorescent scale inhibitor, generally focusing on polyacrylate and
poly(maleic acid) [22,23]. Moriarty performed 8-allyloxy-1,3,6-pyrene
trisulfonic acid trisodium salt (APTA) uorescent monomers. Hydrophilic of APTA is strong because of sulfoacid hydrophilic groups [24].
In our previous work, no phosphate and nitrogen free scale inhibitor
(APECn, APELn, APEGPG\COOH) for cooling water systems were prepared from allyloxy polyethoxy ether, NaOH, and chloracetic acid,
glycidol or succinic anhydride (SA) and allylpolyethoxy carboxylate, a
double-hydrophilic block copolymer, has a high molecular weight and
the (\COOH) anionic active groups are at leteral and exposed
[2528]. However, the preparation process still has two defects:
(a) chloracetic acid is toxic, and harmful to human body and environment and (b) glycidol and succinic anhydride (SA) are very expensive,
and difcult to turn into a large-scale business. Thus, new types of
double-hydrophilic block copolymer need to be developed.
In this contribution, a new calcium carbonate scaling inhibitor was
studied. The purpose of the present study presents the results of no
phosphate and nitrogen free chemicals study that was undertaken to investigate the ability of new inhibitors (Maleic anhydrideOxalic acid
Allypolyethoxy carboxylate (MAAPEM)) to inhibit the scale problems
found in cooling water systems. MAAPEMAPTA compensates the
weaknesses of AAAPES which contain nitrogen and cannot be
monitored.

2. Experimental

2.2. Preparation of APEM, APTA and MAAPEMAPTA

The carboxylic acid functionalization of the surface hydroxyl groups
was realized by reaction with oxalic acid (OA). The synthesis procedure
of APEM is shown in Fig. 1. APTA was synthesized according to Moriarty
[24]. Synthesis procedure of APTA from pyranine and allyl chloride is
shown in Fig. 2. The synthesis procedure of MAAPEMAPTA from
MA, APEM and APTA is shown in Fig. 3.
2.3. Measurements
The samples were analyzed using a FT-IR spectroscopy (VECTOR-22,
Bruker Co., Germany) in the region of 4000500 cm1. Prior to the measurement, the samples were dried under vacuum until reaching to a
constant weight. The dried samples were pressed into the powder,
mixed with KBr powder, and then compressed to make a pellet for FTIR characterization. Structures of APEG, APEM and MAAPEMAPTA
were also explored by a Bruker NMR analyzer (AVANCE AV-500, Bruker,
Switzerland) operating at 500 MHz.
Thermogravimetric analysis (TGA) was performed on samples at
temperatures ranging from 25 C to 750 C. Such signals were obtained
at a heating rate of 20 C/min in air using a Perkin-Elmer Derivatograph
instrument. X-ray diffraction (XRD) patterns of the CaCO3 crystals were
recorded on a Rigaku D/max 2400 X-ray powder diffractometer with Cu
K ( = 1.5406) radiation (40 kV, 120 mA).
Scanning electron microscopy (SEM) images were recorded using
a eld emission scanning electron microscope (S-3400 N HITECH
SEM). Prior to imaging by SEM, the scale samples were sputtered
with a thin layer of gold. The shape of CaCO 3 scale was observed
with a transmission electron microscope (TEM, JEM-2100SX,
Japan). Fluorescence measurements were carried out on a luminescence spectrometry (LS-55, Perkin-Elmer, UK) with a xenon lamp
as a light.

2.1. Materials

2.4. Precipitation of calcium carbonate experiments

8-hydroxy-1,3,6-pyrene trisulfonic acid trisodium salt (pyranine)

was purchased from Xuhua Chemical (Shanghai, China). Allyloxy
polyethoxy ether (APEG) was purchased from Zhongshan Chemical
(Nanjing, Jiangsu, China). Other reagents such as maleic anhydride,
oxalic acid, potassium peroxydisulfate, allyl chloride, and ammonium
persulfate are of AR grade and were obtained from Zhongdong Chemical
Reagent (Nanjing, Jiangsu, China). Poly(acrylic acid) (PAA, 1800 MW),
hydrolyzed polymaleic acid (HPMA, 600 MW), polyepoxysuccinic acid
(PESA, 1500 MW), and acrylic acidhydroxypropylacrylate (AAHPA
or T-225, 2100 MW) were of technical grade and were supplied by
Jiangsu Jianghai Chemical Co., Ltd. Distilled water was used for all the
studies.

All precipitation experiments were carried out in ask tests and

all inhibitor dosages given below are on a dry-inhibitor basis. Tests
of the inhibitors were carried out using supersaturated solutions of
CaCO3 at 60 C. The solutions were prepared by dissolving in distilled
water reagent grade CaCl 2 and NaHCO 3 (Zhongdong Chemical Reagent Co.) at equivalent concentrations of 24 milli-equivalent/L
(cooling water code GB/T 166322008). The supersaturation level
of the solutions corresponded to a Langelier Index of 2.1. Each inhibition test was carried out in a ask of 500 mL immersed in a
temperature-controlled bath for 10 h. Precipitation of CaCO 3 was
monitored by analyzing aliquots of the ltered (0.22 m) solution
for Ca2 + ions using EDTA complexometry as specied in code GB/T

Fig. 2. Preparation of APTA.

H. Wang et al. / Desalination 340 (2014) 110

154522009. Inhibitor efciency was calculated from the following

equation:
h

i
h
i
Ca2
Ca2
final

blank  100%
inhibition %  2 
Ca initial Ca2 blank

+
1502

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

the presence of inhibitor after calcium carbonate supersaturated solutions were heated for 10.0 h at 60 C, [Ca2 +]blank is the concentration of Ca 2 + ions in the ltrate in the absence of inhibitor after
calcium carbonate supersaturated solutions were heated for 10.0 h
at 60 C, and [Ca2 +]initial is the concentration of Ca2 + ions at the beginning of the experiment.

3449

+
1046
APTA

500

1000

1500

2000

2500

3000

3500

4000

Wavenumbers (cm-1)
2.5. Excitation, emission wavelength measurement and detection of uorescent
intensity of inhibitor
Excitation and emission wavelengths of APTA and MAAPEMAPTA
were all measured at ex = 402 nm (10 nm slid width) and em =
430 nm (5 nm slid width), respectively. The excitation and emission
wavelengths were chosen to be the same as the excitation and emission wavelength of pyranine. 5 10 8 mol/L APTA distilled water
solution was prepared and MAAPEMAPTA was dissolved in quantum
sufcient distilled water and concentration of APTA in MAAPEMAPTA
solution was also 5 108 mol/L. A serial concentration of MAAPEM
APTA sample should reect a corresponding serial of the uorescence
intensity. Prepared 2, 4, 6, 8, 10, 12, 14, 16, 18 mg/L MAAPEMAPTA
aqueous solution samples to estimated MAAPEMAPTA uorescent
intensity response to their concentration.
3. Results and discussion
3.1. FT-IR and 1H NMR measurements
The FT-IR spectra of APTA, PEM and MAAPEMAPTA are exhibited
in Figs. 4 and 5. APTA (FT-IR, cm1): 1046 (alkyl oxide characteristic absorption of APTA), 1239 (fragrant ether characteristic absorption),
14501630 (aromatic compound absorption band), 1657 (C_C
stretching vibration), 3449 (O\H stretching vibration). The C_C

Fig. 4. FT-IR spectra of APTA.

stretching shows a sharp intense peak at 1657 cm1. The FT-IR proves
that the synthesized monomer has the anticipated structure. The
1743 cm 1 strong intensity absorption peak (\C_O) in curve
Fig. 5(a) reveals clearly that APEM has been synthesized successfully.
The fact that the (\C_C\) stretching vibration at 1642 cm1 appears
in Fig. 5(a) but disappears completely in Fig. 5(b) reveals that free radical polymerization between MA, APEM and APTA has happened.
Fig. 6 is 1H NMR of pyranine (a) and APTA (b), pyranine ((CD3)2SO,
ppm): 2.402.60 (solvent residual peak of (CD3)2SO), 8.109.15 (six
protons of benzene ring in pyranine), and 10.63 (\OH, active hydrogen
in pyranine) (Fig. 6(a)). APTA ((CD3)2SO, ppm): 2.402.60 (solvent
residual peak of (CD3)2SO), 4.976.33 (CH2_CH\CH2\, propenyl protons), and 8.109.15 (six protons of benzene ring in APTA) (Fig. 6(b)).
APEG (Fig. 7(a)) ((CD3)2SO, ppm): 2.50 (solvent residual peak of
(CD3)2SO), 3.003.80 (\OCH2CH2\, ether groups), 3.806.00 (CH2CH\CH2\, propenyl protons), and 4.404.60 (\OH, active hydrogen in APEG). APEM (Fig. 7(b)) ((CD 3) 2 SO, ppm): 2.50 (solvent
residual peak of (CD3)2SO), 3.503.90 (\OCH2CH2\, ether groups),
and 4.106.00 (CH2_CH\CH2\, propenyl protons). The complete
disappearance of 4.404.60 ppm (\OH) active hydrogen in (a) proves
that\OH in APEG has been entirely replaced by\COCOOH. 3.80

Fig. 3. Preparation of MAAPEMAPTA.

H. Wang et al. / Desalination 340 (2014) 110

degradation of APEG, APEM and MAAPEMAPTA all proceeded in

three or four stages. The rst decomposition stage was assigned in the
removal of the volatile matter present in these samples, such as
entrapped moisture or extraction solvent. The greatest percentage decomposition of APEG and APEM occurred in the second stage
(180400 C), as indicated by the corresponding weight loss values. It
may be attributed to cracking and gasication at high temperatures. It
is indicated that free radical polymerization can effectively enhance
thermal stability of copolymer.

(b)

500

1000

1500

2000

2500

3000

3500

4000

4500

3.3. Excitation and emission properties of APTA and MAAPEMAPTA

(a)

Excitation and emission wavelengths of APTA and MAAPEMAPTA

are shown in Figs. 9 and 10. It can be achieved by the gure that excitation and emission wavelengths of APTA and MAAPEMAPTA are also
402 nm and 430 nm. Chromophore of APTA and MAAPEMAPTA are
all pyranine so MAAPEMAPTA and APTA have the same excitation
and emission wavelengths as pyranine. Excitation spectra and emission
spectra of MAAPEMAPTA show good mirror-image relationship as
APTA. It is obvious that molecule structure of uorescent conguration
changed a little from monomer to copolymer. The uorescence intensity
of MAAPEMAPTA increased compared with APTA after copolymerization because of the form of hydrogen bonding [29].

1642

1743
1500

2000

2500

Wavenumbers

3000

3500

4000

4500

(cm-1)

Fig. 5. FT-IR spectra of (a)APEM and (b) MAAPEMAPTA.

6.00 ppm in (b) double bond absorption peaks completely disappeared

in (c). This reveals that free radical polymerization among MA, APEM,
and APTA has happened.
3.2. Characterization by TGA

The uorescence intensity spectra recorded for 218 mg/L aqueous

solutions of MAAPEMAPTA at varying concentrations are shown in
Fig. 11. Also the result of linearity testing between MAAPEMAPTA
uorescence intensity and their concentration is shown in Fig. 12.
Fluorescence intensity was good linear to MAAPEMAPTA concentration in the range of 218 mg/L which is common dosage scope to the

9.0

8.291
8.169

2.509
2.505

(a)

15.7 5

2.15

4.00

10.0

8.884

8.995
8.987
8.975

Thermogravimetric analysis (TGA) was used to obtain further

information on the structures of APEG, APEM and MAAPEMAPTA.
The corresponding TGA are depicted in Fig. 8. The gure shows that

3.4. Response of uorescent intensity over a range of MAAPEMAPTA

8.0

7.0

6.0

5.0

4.0

3.0

2.0

1.0

6.311
6.301
6.290
6.280
6.277
6.266
6.255
6.246
5.622
5.619
5.588
5.584

8.217

8.966
8.946
8.415
8.396

9.041

9.144
9.125

ppm

7.0

6.0

15.60

8.0

4.36

9.0

1.00

5.84

10.0

(b)

2.548
2.502

1000

4.981
4.971

500

5.396
5.393
5.375
5.372

5.0

4.0

3.0

2.0

1.0

ppm
1

Fig. 6. The H NMR spectra of (a) pyranine and (b) APTA.

2.497

3.508
3.421
3.344

2.505
2.502
2.498

3.427
3.416
3.406

3.513
3.451

3.681
3.672
3.663

2.508

3.516

7.0

6.0

5.0

4.0

8.46

79.49

8.0

ppm

2.0
3.347

5.111

3.942
4.356
4.347
4.338

5.121

5.142

5.224

4.307
4.298
4.288
3.950
3.941

3.0

8.317
8.298
8.173

8.888

9.040
9.021
9.001
8.994
8.981

4.0

2.10

4.00

9.0

ppm

1.0

1.10

2.18

1.96

5.0

2.0

26.30

5.259

5.278

5.881
5.869

3.0

2.25

1.00

1.14

6.0

0.29

4.0

1.16

(b)

20.5 4

5.0

1.69

0.05

1.00

2.09

1.14

6.0

(c)

4.546

5.146

5.212

5.835
5.820
5.270

(a)

5.926
5.910
5.891
5.873
5.855

H. Wang et al. / Desalination 340 (2014) 110

3.0

2.0

1.0
ppm

Fig. 7. The H NMR spectra of (a) APEG, (b) APEM and (c) MA-APEM-APTA.

inhibitors. The relationship between MAAPEMAPTA concentration

and uorescence intensity provided an exceptionally linear response
[correlation coefcient R2 = 0.9973]. This positive linear relationship
can be used to measure MAAPEMAPTA concentration accurately. The
dosage change of MAAPEMAPTA is pointed out by the uorescence

spectra of MAAPEMAPTA. This optical technique is able to characterize

early corrosion and to quantify corrosion defects. The detection limit of
MAAPEMAPTA is 0.79 mg/L according to the detection limit formula:
Dr = 3 / k, where is 11 times the determination of blank solution's
standard deviation and k is the slope of calibration curve [30].

105

Excitied spectrum
Emitted spectrum
Fluorescent Intensity

75

Weight (%)

300

APEG
APEM
MA-APEM-APTA

90

60
45
30
15

250

200

150

100

0
0

100

200

300

400

500

600

700

Temperature (oC)
Fig. 8. TGA curves for APEG, APEM and MAAPEMAPTA.

800

380

400

420

440

460

480

Wavelength/nm
Fig. 9. Excitation and emission wavelength of APTA.

500

H. Wang et al. / Desalination 340 (2014) 110

700

700

600

600

Fluorescent Intensity

Fluorescent Intensity

500
400
300

Excited spectrum
Emitted spectrum

200
100
380

Fi = 67.172C + 33.051
2

R = 0.9973

500
400
300
200
100

400

420

440

460

480

500

Wavelength/nm

Fig. 10. Excitation and emission wavelength of MAAPEMAPTA.

3.5. Inuence of MAAPEM and MAAPEMAPTA dosage on CaCO3

inhibition
The scale inhibition performance of MAAPEM and MAAPEM
APTA in simulated scale inhibition solution at different concentrations
of inhibitor was shown in Table 1. For CaCO3 inhibition, MAAPEM
APTA was weakly inferior to MAAPEM, but 93.5% inhibition were obtained at the concentration of 8 mg/L. In addition, although APTA
group does not do very well in water-soluble, their incorporation had
a slight inhibitive effect on CaCO3 because the molar fraction of 0.5% of
APTA group in MAAPEMAPTA is much lower as mentioned above
and it is enough to work.
Furthermore, to understand the performance of MAAPEMAPTA,
some inhibition experiments were conducted with commercial inhibitor at the identical conditions. Compared to MAAPEMAPTA, a recent
most effective inhibitor, MAAPEMAPTA had superior ability to inhibitor the CaCO3 scale, with 79.6% inhibition at a level of 6 mg/L, whereas
it is 55.8% for T-225 at the same dosage (the best inhibitor among
them). So when compared to these nonphosphorus inhibitors, CaCO3
inhibition of MAAPEMAPTA is much better than that of T-225,
HPMA, PAA, PESA at the same dosage. It can be shown that the order
of preventing the precipitation from ask tests was MAAPEM N MA
APEMAPTA N T-225 N PESA N PAA HPMA.
Also, we can found that PAA and HPMA containing carboxyl groups
and possessing molecular structure to MAAPEMAPTA inhibitor but
can hardly control CaCO3 scale even at a high dosage. It may be that
the side-chain polyethylene (PEG) segments of APEM and carboxyl
groups of MA might play an important role during the control of calcium

700
2mg/L

600

Fluorescent Intensity

4mg/L

500

6mg/L

10

12

14

16

18

20

Concentration (mg/L)
Fig. 12. Linearity of the uorescence intensity (Fi) with the concentration (C) of MA
APEMAPTA.

carbonate scales. Taking Table 1 into account, it can conclude that the
studied copolymer MAAPEMAPTA not only to solve the water eutrophication problems caused by phosphorus but because of its signicant
inhibition efciency in cooling water systems.

3.6. Inuence of solution property on CaCO3 inhibition

Solution properties have a great inuence on the CaCO3 inhibition. In
order to optimize parameters of the cooling water system on an industrial scale, we investigated the effect of the solution parameters on the
CaCO3 inhibition of MAAPEMAPTA.
From Fig. 13, it can be found that Ca2+ concentration and temperature had a big effect on MAAPEMAPTA, they were in a similar linear
decreasing trend with the raise of Ca2+ concentration and temperature.
Fig. 13(a) indicates that MAAPEMAPTA provides CaCO3 inhibition
under conditions of water with a much higher hardness. If Ca2+ concentration increased by 50%, the inhibition efciency declined by 10.2%. The
results indicated that MAAPEMAPTA was a relatively effective inhibitor which depended slightly on Ca2+ concentration. Fig. 13(b) clearly
demonstrates the superior thermal stability of the MAAPEMAPTA copolymers. When increasing the solution temperature from 70 to 90 C,
MAAPEMAPTA retains most of its activity, with only 23% loss in
CaCO3 inhibition. Particularly, the inhibition rate of the MAAPEM
APTA was reduced by a big margin when the temperature was higher
than 80 C. The inhibition performance was reduced sharply. But
when at a temperature of 5070 C, and at usual temperature values
of industry cooling water systems, copolymer still shows superior
CaCO3 inhibition. So we must sensitive the effect of the temperature
on a scale inhibition. Thus, the incorporation of the high performance
scale inhibitor MAAPEMAPTA into recycling water promotes a better
overall system performance.

8mg/L

400

10mg/L
12mg/L

300

14mg/L

200

Table 1
Comparison of CaCO3 inhibition.

16mg/L

Inhibition on CaCO3 (%)

18mg/L

Inhibitor type

100
0

420

440

460

480

500

Wavelength(nm)
Fig. 11. Fluorescence emission spectra of 218 mg/L MAAPEMAPTA solutions.

MAAPEM
MAAPEMAPTA
T-225
HPMA
PAA
PESA

Dosage (mg/L)
2

10

12

14

16

14.5
15.2
19.8
13.1
15.5
16.7

50.7
52.7
35.2
18.9
33.5
26.8

83.3
79.6
55.8
31.3
40.1
40.5

97.5
93.5
60.5
47.6
55.7
53.4

98.1
97.6
73.4
62.1
63.2
65.5

98.3
95.4
80.5
70.2
70.1
79.2

97.1
96.9
82.9
73.5
80.6
81.1

97.8
96.5
81.6
71.6
81.3
84.2

H. Wang et al. / Desalination 340 (2014) 110

110

Inhibition of CaCO3 (%)

(a)
100

90

80

70

60

300

600

900

Concentration of

Ca2+(

1200

1500

mg/L)

100

(b)
Inhibition of CaCO3 (%)

95
90

corners of the crystals disappeared completely (Fig. 14(b)). The precipitates collected from the experiments without MAAPEMAPTA added
showed the characteristic of regular shaped rhombohedra, and the particles' size was uniform (Fig. 15(a)). In the presence of MAAPEMAPTA
in 6 mg/L, the CaCO3 scale lost its unabridged structure, and the decrescent particles were distributed randomly (Fig. 15(b)).
The X-ray diffraction pattern of the crystals obtained in the absence
and presence of copolymer is given in Fig. 16. In the absence of MA
APEMAPTA copolymer, calcite is the main crystal form (Fig. 16(a)).
Fig. 16(b) shows the X-ray diffraction spectrum for CaCO3 precipitate
in the presence of MAAPEMAPTA copolymer, while one could clearly
observe a series of quite strong diffraction peaks of 2 at 24.9, 27.2,
32.8, 43.9, and 49.1 corresponding to Miller indices (110), (112),
(114), (300), and (118), typical of vaterite (JCPDS No. 330286 in
space group P63/mmc) [3133]. The change of crystal forms was also
conrmed by FT-IR spectra. As shown by the curve in Fig. 17, the
peaks at 711 cm1 reect the feature of calcite, and the peaks at
742 cm1 reect the feature of vaterite [34]. It was found that thermodynamically unstable vaterite could be stabilized kinetically in the
presence of the MAAPEMAPTA copolymer. Calcite is the most thermodynamically stable, and vaterite is the least stable form in the three
polymorphic forms of CaCO3 [35]. The above analysis shows that some
calcite crystals are changed into another CaCO3 structure, formed in
vaterite after adding MAAPEMAPTA. As a result, the impact on heat
transfer can be prevented and the scale inhibition effect can be acquired.

85

3.8. Inhibition mechanism toward CaCO3 scale

80
75
70
65

50

60

70

80

90

Temperature (oC)
Fig. 13. CaCO3 inhibition at a level of 8 mg/L MAAPEMAPTA as a function of solution (a)
Ca2+ concentration and (b) temperature.

3.7. Characterization of calcium carbonate scale

The collected CaCO3 crystal was characterized by SEM and TEM analyses. The results are shown in Figs. 14 and 15. As shown in Fig. 14(a), integrated symmetrical monoclinic hexahedron calcite crystal was
observed. In contrast, the morphologies of the CaCO3 changed to some
different extent when the MAAPEMAPTA was used. When the MA
APEMAPTA concentration increased to 6 mg/L, sharp edges and acute

MAAPEMAPTA is a structurally well-dened biblock copolymer,

depicted in Fig. 18; one block is PMA, and the other is APEMAPTA. It
is well known that PMA chain in MAAPEMAPTA could react with
Ca2+ or crystal nucleus of CaCO3, and then affect the growth of CaCO3
crystals. Both PMA and PEG (marked with green ribbons in Fig. 18) segments are hydrophilic blocks and exist randomly in water. When Ca2+
are added into copolymer solutions, carboxyl groups in MAAPEM
APTA matrixes can recognize and encapsulate or react with positively
charged calcium ions either in solutions or on the surface of inorganic
minerals, such as CaCO3, Ca3(PO4)2 and CaSO4 [36,37]. Encapsulation
or interaction, between Ca2+ and carboxyl groups, leads to the spontaneous formation of MAAPEMAPTACa complexes (Encapsulation
zone). At the same time, water-compatible PEG segments have the
very strong hydrophilicity and thus increase its solubility in water
(highly dissolved solid particles zone). In addition, the long PEG side
chains in MAAPEMAPTA matrix result in steric and electrostatic repulsion. The hypothesis of inhibition mechanism is consistent with
those of Antonia et al., who reported that cationic polymers exhibited
higher inhibitory performance resulting from the interactions between
polycation (polymer) and polyanion (silica) [38].

Fig. 14. SEM photographs for the CaCO3 (a) and with the presence of MAAPEMAPTA (b) 6 mg/L.

H. Wang et al. / Desalination 340 (2014) 110

Fig. 15. TEM photographs for the CaCO3 (a) and with the presence of MAAPEMAPTA (b) 6 mg/L.

The scale process of microsolubility salts (CaCO3) in cooling water

systems is just the process of crystal formation, CaCO3 crystallization
consists of two stages: nucleation and growth. Another accepted inhibition mechanism is inhibitor can adsorption on the scale surface causes
defects during the growth of scale nuclei [39]. The relationship between
time and the MAAPEMAPTA copolymer concentration in experiment
solution can be seen in Table 2. MAAPEMAPTA concentration
decrease indicates that the inhibition mechanism of CaCO3 is by the adsorption of inhibitor on crystal nuclei. Part of the MAAPEMAPTA copolymer particles had embedded in the lattice of CaCO3 micro-crystal
particles and precipitated along with CaCO3. Also the result indicates
that with the increase of inhibitor concentration in the solution, residual
inhibitor concentration increased. The more inhibitor added in the
water solution, the carboxyl groups in MAAPEMAPTA can be encapsulated or react with more Ca2 + to spontaneously form MAAPEM
APTACa2 + complexes. Nucleation stage of the CaCO3 will be hardly
formed in the experiment solution. Hence, the inhibitor adsorbed on
the growth sites of the nuclei decreased.
As a result, the existing minerals do not precipitate with MAAPEM
APTA through its excellent ability to disperse solid particles such as
CaCO3 scales. Thus, MAAPEMAPTA possesses excellent ability to control CaCO3 scale.

4. Conclusions
This study investigated the effect of a copolymer on the calcium carbonate inhibition. Water-soluble monomer APEM was produced from
APEG and oxalic acid by carboxylic acid functionalization method. Fluorescent monomer APTA was prepared from pyranine and allyl chloride.
Structures of APEG, APEM, and APTA were identied by FT-IR and 1H
NMR. Fluorescent-tagged no carbonate and nitrogen free calcium carbonate inhibitor MAAPEMAPTA was successfully synthesized by
free polymerization of MA, APEM, and APTA. FT-IR and 1H NMR identied that MAAPEMAPTA has the expected structures. The dosage of
MAAPEMAPTA copolymer has a strong effect on the formation of calcium carbonate precipitation. It can be concluded that the order of
preventing the precipitation from ask tests was MAAPEM N MA
APEMAPTA N T-225 N PESA N PAA HPMA.
Excitation and emission spectra of APTA and MAAPEMAPTA have
been detected readily with a uorospectro photometer and they show
good mirror symmetry relations. MAAPEMAPTA detection limit is
0.79 mg/L according to the detection limit formula. Good relationship
between MAAPEMAPTA uorescent intensity and its dosage (the correlation coefcient R2 = 0.9973) ensures that MAAPEMAPTA is a
valuable indicator for cooling water system performance. The new active polymer test method provides an easy, quick, and accurate method
to determine polymer consumption.

(b)

Vaterite

b
Vaterite

(a)

Calcite

a
Calcite
711

20

25

30

35

40

45

50

2 (Degree)
Fig. 16. XRD image of the CaCO3 crystal formed in the absence of MAAPEMAPTA (a) and
with the presence of MAAPEMAPTA (b) 6 mg/L.

600

1080

742
800

1000

1200

Wavenumber cm-1
Fig. 17. FT-IR image of the CaCO3 crystal formed in the absence of MAAPEMAPTA (a)
and with the presence of MAAPEMAPTA (b) 6 mg/L.

H. Wang et al. / Desalination 340 (2014) 110

Fig. 18. Encapsulation calcium irons route via carboxyl groups.

SEM images indicate that MAAPEMAPTA changes highly the morphology and size of calcium carbonate crystals during the inhibition
process. The TEM mechanism of the scale shape effect process is similar
to the SEM. Also this nding was conrmed by studying the crystal
habits of CaCO3 in the absence or presence of MAAPEMAPTA using
XRD and FT-IR analyses.

Acknowledgments
This work was supported by the Prospective Joint Research Project of
Jiangsu Province (BY2012196); the National Natural Science Foundation of China (51077013); special funds for Jiangsu Province Scientic
and Technological Achievements Projects of China (BA2011086); the
Fundamental Research Funds for the Central Universities; Scientic Innovation Research Foundation of College Graduate in Jiangsu Province
(CXLX13-107, CXZZ13-0091); and Program for Training of 333 HighLevel Talent, Jiangsu Province of China (BRA2010033).

Table 2
The relationship between time and the MAAPEMAPTA copolymer concentration in
experiment solution.
MAAPEMAPTA copolymer concentration in experiment solution
Time (h)

2
4
6
8
10

Dosage (mg/L, initial concentration)

2

10

14

16

1.89
1.65
0.98
0.82
0.77

5.27
5.03
4.87
3.96

9.76
9.54
9.24
9.15

13.59
13.50
13.46
13.34

15.81
15.79
15.67
15.62

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