ARTICLE

pubs.acs.org/IECR

Inhibition of Ca3(PO4)2, CaCO3, and CaSO4 Precipitation for Industrial

Recycling Water
Fu Change,†,‡ Zhou Yuming,*,† Liu Guangqing,† Huang Jingyi,† Sun Wei,§ and Wu Wendao§
†
School of Chemistry and Chemical Engineering, Southeast University, Nanjing 211189, P. R. China
‡
Nanjing College of Chemical Technology, Nanjing, 210048, P. R. China
§
Jiangsu Jianghai Chemical Co., Ltd., Changzhou 213116, Jiangsu, P. R. China

ABSTRACT: In an attempt to control Ca3(PO4)2, CaCO3, and CaSO4 deposits in industrial recycling water systems, an acrylic acid
(AA)
allylpolyethoxy carboxylate (APEC) copolymer was examined as a nonphosphorus inhibitor. The synthesized AA
APEC
copolymer was characterized by FT-IR. The performance of AA
APEC on inhibition of Ca3(PO4)2, CaCO3, and CaSO4
precipitation was compared with that of current commercial inhibitors. It was shown that AA
APEC exhibited excellent ability to
control inorganic minerals, with approximately 82.88% CaSO4 inhibition and 99.89% Ca3(PO4)2 inhibition at levels of 3 and 6 mg/L
AA
APEC, respectively. AA
APEC also displayed ability to prevent the formation of CaCO3 scales. Transmission electron
microscopy (TEM) images indicated that the outstanding performance of AA
APEC on Ca3(PO4)2 inhibition resulted from a
decrease in size of Ca3(PO4)2 solid particles thereby dispersing these particles throughout a fluid, while CaCO3 inhibition was
attributed to the formation of ribbon-shaped structures and CaSO4 inhibition resulted from loose CaSO4 crystallites speculated on
scanning electron microscopy (SEM) images. The proposed inhibition mechanism suggests the formation of complexes between
the side-chain carboxyl groups of AA
APEC and calcium ions on the surface of inorganic minerals, and the excellent solubility of
complexes resulted from a number of hydrophilic polyethylene glycol (PEG) segments.

1. INTRODUCTION nonphosphorus and effective to control the formation of

For environmental and economic reasons, a greater number of calcium-phosphate, calcium-carbonate, and also calcium-
cycles for industrial water should be used. However, it cannot be sulfate deposits.
realized without development of scale control methods.1
3 The Recently, Kessler19 reported a novel inhibitor for calcium-
potential of mineral precipitation continues to be by far the most phosphate deposits. It is a copolymer of maleic anhydride (MA)

costly design and an operating problem in recycling-water ammonium allylpolyethoxy sulfate (APES). Although it possesses
systems.4
6 Alkaline scales such as calcium carbonate can be excellent calcium phosphate inhibition at a low dosage, it cannot
easily controlled by acidifying and maintaining pH below 7.5. control the formation of calcium-sulfate scales until the dosage
Due to its low cost, sulfuric acid is usually used for pH control exceeds 32 mg/L, and it also cannot prevent precipitation of
thereby increasing the potential of calcium-sulfate scale calcium carbonate at any levels of dosage. The aim of the present
formation.1,2,7 In addition, using sulfuric acid to control pH work is to provide a nonphosphorus copolymer of acrylic acid
can also cause system corrosion, which in turn can be an (AA)
allylpolyethoxy carboxylate (APEC) as an ideal inorganic
additional source of fouling.8,9 Thus, an ideal scale inhibitor mineral inhibitor. Such an inhibitor can control both calcium-
would be able to prevent both calcium-carbonate precipitation at carbonate scales at pH 9.0 and calcium-sulfate scales at pH 7.0. In
high pH and calcium-sulfate precipitation at low pH (neutral or the presence of excessive calcium ions and orthophosphates, it
slightly acidic). also can prevent the precipitation of calcium phosphate.
In industrial recycling water systems, another troublesome
issue is the precipitation of corrosion products.5,8 Phosphonates, 2. EXPERIMENTAL SECTION
such as polyamino polyether methylenephosphonate (PAPEMP),
1-hydroxyethylidine-1,1-diphosphonic acid (HEDP), and 2.1. Materials and Characterization. APEC, APES, and
2-phosphonobutane-1,2,4-tricarboxylic acid (PBTC) are used MA
APES were synthesized in our laboratory according to
to prevent mineral formation and/or metallic corrosion by earlier publications.19,20 Acrylic acid (AA), MA, and ammonium
creating protective films on metal surfaces of industrial equip- persulfate employed were analytically pure grade and supplied
ment.9
14 However, phosphonates can create serious problems by Zhongdong Chemical Reagent Co., Ltd. (Nanjing, Jiangsu,
such as insolubility of phosphonate complexes, and they are also P. R. China). Commercial inhibitors of poly(acrylic acid) (PAA,
susceptible to breakdown to form orthophosphates under the 1800 MW), hydrolyzed polymaleic acid (HPMA, 600 MW),
influence of hydrolysis and/or chlorination thereby increasing
the potential of formation of calcium-phosphate deposits in the Received: January 10, 2011
presence of excessive amounts of calcium.15
17 In addition, Accepted: August 20, 2011
phosphonates, when reverted to orthophosphates, are potential Revised: July 9, 2011
nutrients for algae.18 Thus, an ideal scale inhibitor would be Published: August 20, 2011

r 2011 American Chemical Society 10393 dx.doi.org/10.1021/ie200051r | Ind. Eng. Chem. Res. 2011, 50, 10393–10399
Industrial & Engineering Chemistry Research ARTICLE

Scheme 1. Synthesis of AA
APEC The prepared solutions, 250 mL of CaC12 (13 600 mg/L Ca2+)
and 250 mL of Na2SO4 (14 200 mg/L SO42
), were kept in
separate glass bottles at room temperature for 5 h to stabilize
their temperature. After that time, at the beginning of experi-
ments, these solutions were mixed in a flask of 500-mL capacity
immersed in a temperature-controlled bath. To avoid the con-
centration of the solution by evaporation especially at a high
temperature, we condensed the vapor by means of a cooler.
Precipitation of these calcium-sulfate supersaturated solutions
polyepoxysuccinic acid (PESA, 1500 MW), acrylic acid
hydrox-
was monitored after these solutions were heated for 6.0 h at
ypropyl acrylate (AA
HPA or T-225, 2100 MW), PAPEMP 80 °C by analyzing aliquots of the filtered (0.22 μm) solutions for
(615 MW), HEDP(206 MW) and PBTC (270 MW) were Ca2+ ions concentration by using EDTA complexometry titra-
technical grade and supplied by Jiangsu Jianghai Chemical Co., tion according to the national standard of P. R. China concerning
Ltd. (Changzhou, Jiangsu, P. R. China). Distilled water was used the code for the design of industrial recirculating cooling-water
in all the studies. treatment (GB/T 15452-2009). The pH of the calcium-sulfate
Fourier-transform infrared (FT-IR) spectra were measured on supersaturated solutions was adjusted to 7.0 by using dilute
a Bruker FT-IR analyzer (VECTOR-22, Bruker Co., Germany) solutions of sodium hydroxide and/or hydrochloric acid and kept
by using the KBr-pellet method (compressed powder). The constant with borax buffer solutions. In another series of experi-
shapes of calcium-phosphate and calcium-carbonate scales were ments under the same conditions as described above, the
observed with a transmission electron microscope (TEM, JEM- precipitation of calcium-sulfate solutions was studied in the
2100SX, Japan). The shape of calcium-sulfate scales was ob- presence of chemical scaling inhibitors added to the CaC12
served with a scanning electron microscope (SEM, S-3400N, solutions before mixing with Na2SO4 solutions. A number of
HITECH, Japan). inhibitors of AA
APEC, MA
APES, PAA, HPMA, PESA,
2.2. Experimental Procedure. 2.2.1. Synthesis of AA
APEC. T-225, PAPEMP, HEDP, and PBTC were tested.
A 5-neck round-bottom flask equipped with a thermometer and a Inhibitor efficiency as a calcium
sulfate inhibitor was calcu-
magnetic stirrer was charged with 70 mL of distilled water and 40 lated by using the following equation:
g of AA, and heated to 70 °C with stirring under nitrogen.
Subsequently, 40 g of APEC in 18 mL of distilled water ½Ca2þ final
½Ca2þ blank
(APEC/AA mass ratio = 1:1) and the initiator solution (3.0 g Inhibition ð%Þ ¼  100%
½Ca2þ initial
½Ca2þ blank
of ammonium persulfate in 18 mL of distilled water) were added
separately at constant flow rates over a period of 1.0 h. The
where [Ca2+]final is concentration of Ca2+ ions in the filtrate in
reaction mixture was heated to 80 °C and maintained at this
the presence of inhibitor after calcium-sulfate supersaturated
temperature for a further 1.5 h, to ultimately afford an aqueous
solutions were heated for 6.0 h at 80 °C, [Ca2+]blank is concen-
copolymer solution containing approximately 35% solid. This
tration of Ca2+ ions in the filtrate in the absence of inhibitor after
product was decanted into a 10-fold volume of acetone with calcium-sulfate supersaturated solutions were heated for 6.0 h at
stirring. The resulting insoluble products were filtered and 80 °C, and [Ca2+]initial is concentration of Ca2+ ions at the
extracted in a Soxhlet extractor for 20.0 h to remove the beginning of the experiment.
remaining AA and APEC. The crude products were dried in a Procedure of calcium-carbonate precipitation experiments was
vacuum oven to constant weight to yield the desired AA
APEC also carried out similarly to calcium-sulfate precipitation experi-
as a reddish viscous liquid. The synthesis procedure employed for ments, except that the prepared solutions, 250 mL of CaC12
the preparation of AA
APEC from AA and APEC is shown in (13 600 mg/L Ca2+) and 250 mL of Na2SO4 (14 200 mg/L
Scheme 1. SO42
), were changed into solutions of 250 mL of CaC12 (480
2.2.2. Precipitation Conditions. All precipitation experiments mg/L Ca2+) and 250 mL of NaHCO3 (1464 mg/L HCO3
)
were carried out in triplicate and all inhibitor dosages given below according to the national standard of P. R. China concerning the
are on a dry-inhibitor basis. Analytical reagents and A grade code for the design of industrial recirculating cooling-water
glassware were used throughout. Water used was distilled water. treatment (GB/T 16632-2008).
All Ca2+ ions concentration as CaCO3 was standardized through
EDTA titrimetric method. Procedure of calcium-phosphate
3. RESULTS AND DISCUSSION
precipitation experiments was described in an earlier publi-
cation.20 The precipitation experiments were done under 3.1. Characterization of AA
APEC. The FT-IR spectra of
the conditions of 250 mg/L Ca2+, 5 mg/L PO43
, pH = 9.0, APEC and AA
APEC are shown in Figure 1. The fact that the
T = 80 °C, t = 10 h according to the national standard of P. R. (—CdC—) stretching vibration at 1646 cm
1 appears in curve
China concerning the code for the design of industrial recirculat- a, while it disappears completely in curve b reveals that free
ing cooling-water treatment (GB 50050-95). Polymer efficiency radical polymerization between APEC and AA had happened.
as a calcium-phosphate inhibitor was calculated according to a The 1725 cm
1 strong intensity absorption peak (—CdO) in
previous publication.20 curve a and b clearly reveals that both APEC and AA
APEC
Calcium sulfate was precipitated from supersaturated solu- contain carboxyl groups.
tions prepared by mixing of CaCl2 and Na2SO4 solutions 3.2. Effect of Inhibitor on Calcium-Phosphate Scales.
according to the national standard of P. R. China concerning The ability of AA
APEC to control calcium-phosphate deposits
the code for the design of industrial oilfield-water treatment was compared with that of other scale inhibitors as shown in
(SY/T 5673-93). The salts of CaCl2 and Na2SO4 both were Figure 2 and in Table 1. As is apparent from Figure 2, the
analytical reagents from Zhongdong Chemical Reagent Co., Ltd. inhibitor dosage of AA
APEC strongly affected its performance on
10394 dx.doi.org/10.1021/ie200051r |Ind. Eng. Chem. Res. 2011, 50, 10393–10399
Industrial & Engineering Chemistry Research ARTICLE

calcium
phosphate inhibition, and there existed an obvious The data shown in Figure 2 also indicate that, except for
threshold of 6 mg/L AA
APEC. When the dosage of AA
APEC and MA
APES, the other inhibitors investigated
AA
APEC was below 6 mg/L, the inhibition on calcium- display poor calcium phosphate inhibition under the same
phosphate scales substantially increased when the dosage of experimental conditions. Compared to MA
APES, a recent
AA
APEC increased, while it was not variable with the dosage most effective inhibitor for calcium-phosphate scales, AA

when the dosage of AA
APEC exceeded 6 mg/L. The maximum APEC displays superior ability to inhibit the precipitation of
inhibitory power on calcium-phosphate scales was obtained calcium phosphate, with 100% inhibition at a level of 6 mg/L,
when AA
APEC was at a level of 6 mg/L. Similar results were whereas it is 90% for MA
APES at the same dosage. The data
obtained from the data of MA
APES in Figure 2. It should be listed in Table 1 indicate that the calcium phosphate inhibition of
noted that the similar tendency of the dosage on the perfor- the investigated inhibitors is still lower than that of AA
APEC
mance behavior has been reported in earlier studies on even though the inhibitor dosage increases to 35 mg/L, an
polymeric threshold inhibitors.5,17,21,22 unacceptable dosage for economic and environmental reasons.
What deserves to be mentioned is that the calcium phosphate
inhibition of PAPEMP, the most popular calcium phosphate
inhibitor, really increases to 81% at a level of 35 mg/L. However,
PAPEMP belongs to a type of phosphorus inhibitor; on the
contrary, AA
APEC only possesses three elements of carbon,
hydrogen, and oxygen, belonging to a type of nonphosphorus
inhibitor. Furthermore, when compared to AA
APEC, the
dosage of PAPEMP is much higher whereas the inhibition is
much lower.
The presence of scale inhibitors influences not only the growth
rate but also the morphology of the crystal.1,3,8 TEM images of
calcium-phosphate crystals grown in the absence and in the
presence of 4 mg/L AA
APEC are shown in Figure 3, and
indicate that the inhibitor of AA
APEC obviously decreased the
size of calcium-phosphate solid particles thereby dispersing them
Figure 1. FT-IR spectra of APEC (a) and AA
APEC (b). throughout a fluid. In the absence of inhibitor, massive needle-
shaped calcium-phosphate particles of a size of about 200 nm
were obtained (Figure 3a), while in the presence of 4 mg/L
AA
APEC, the irregular calcium-phosphate particles of a size of
about 5
100 nm were produced (Figure 3b).
3.3. Effect of Inhibitor on Calcium-Carbonate Scales.
During the last two decades, investigations on polymeric inhibi-
tors to prevent or retard calcium-carbonate scales have caught
much attention of academic and industrial researchers.7,8 Com-
mon inhibitors evaluated include PAA, HPMA, T-225, PESA,
PBTC, HEDP, PAPEMP, and MA
APES etc., containing acrylic
acid or maleic acid and other monomers with different function-
alities (i.e.,
CONH2,
COOR, SO3H).
In this work, we also studied the influence of these inhibitors
on the prevention of calcium-carbonate scales as shown in
Figure 4. It was suggested that the inhibitor composition has
an interesting impact on inhibitor effectiveness. As effective
inhibitors on calcium-carbonate deposits, phosphonates, such
Figure 2. Inhibition on calcium phosphate as a function of inhibitor as PBTC, HEDP, PAPEMP (marked with solid lines in Figure 4),
dosage. exhibited significant ability to control calcium-carbonate scales,

Table 1. Required Minimum Dosage of Inhibitor for Maximum Ca3(PO4)2 Inhibition

inhibitor abbreviation maximum Ca3(PO4)2 inhibition (%) minimum dosagea (mg/L)

acrylic acid
allylpolyethoxy carboxylate AA
APEC 100 6

maleic anhydride
ammonium allylpolyethoxy sulfate MA
APES 90 6
polyacrylic acid (1800 MW) PAA 73 35
hydrolyzed polymaleic acid (600 MW) HPMA 53 30
polyepoxysuccinic acid PESA 41 8
acrylic acid
hydroxypropyl acrylate T-225 54 12
polyamino polyether methylenephosphonate PAPEMP 81 35
1-hydroxyethylidine-1,1-diphosphonic acid HEDP 71 25
2-phosphonobutane-1,2,4-tricarboxylic acid PBTC 49 12
a
Required minimum dosage to obtain maximum Ca3(PO4)2 inhibition.

10395 dx.doi.org/10.1021/ie200051r |Ind. Eng. Chem. Res. 2011, 50, 10393–10399

Industrial & Engineering Chemistry Research ARTICLE

Figure 3. TEM images of calcium-phosphate crystals: (a) in the

absence of inhibitor and (b) in the presence of 4 mg/L AA
APEC. Figure 5. TEM images of calcium-carbonate crystals: (a) in the absence
of inhibitor and (b) in the presence of 4 mg/L AA
APEC.

structure similar to AA
APEC inhibitor, can hardly control

calcium-carbonate deposits even at a high dosage. This fact
suggests that the side-chain polyethylene glycol (PEG) segments
of APEC and carboxyl groups of AA might play an important role
during the control of calcium-carbonate scales. TEM images in
Figure 5 show the effect of AA
APEC on the crystal morphol-
ogy of calcium carbonate and they indicate that the copolymer of
AA
APEC resulted in the formation of ribbon-shaped structures
thereby preventing the precipitation of calcium carbonate.
3.4. Effect of Inhibitor on Calcium-Sulfate Scales. Calcium-
sulfate scales can be formed by using sulfuric acid to maintain
the pH value of the solution below 7.5 in an attempt to
eliminate alkaline scales such as calcium carbonate and mag-
nesium hydroxide. The performance of AA
APEC on cal-
cium sulfate precipitation, listed in Table 2, was compared
with that of several other calcium-sulfate inhibitors both at a
Figure 4. Inhibition on calcium carbonate as a function of inhibitor
dosage.
level of 2 mg/L and their threshold dosages under the
conditions of 6800 mg/L Ca2+, 7100 mg/L SO42
, pH =
7.0, T = 80 °C, t = 6.0 h.
and their inhibition on calcium carbonate is superior to that of In addition to its outstanding ability to control calcium-
the other investigated nonphosphorus inhibitors including phosphate scales, AA
APEC also exhibited significant ability
AA
APEC (marked with dotted lines in Figure 4). However, to control calcium-sulfate scales, and it was 16 times more
it can be seen from Figure 4 that the copolymer of AA
APEC effective against the formation and precipitation of calcium-
displayed the best ability to control calcium-carbonate deposits sulfate scales than MA
APES at a level of 2 mg/L. The
among nonphosphorus inhibitors investigated, namely, PAA, maximum calcium sulfate inhibition was 83% at a level of 3
HPMA, T-225, PESA, PBTC, and MA
APES. mg/L for AA
APEC, whereas it was 71% at its threshold dosage
It is also worth mentioning that PAA, HPMA, and MA
APES of 32 mg/L for MA
APES. It indicated that AA
APEC has
inhibitors, containing carboxyl groups and possessing molecular excellent ability to control not only calcium-phosphate scales but
10396 dx.doi.org/10.1021/ie200051r |Ind. Eng. Chem. Res. 2011, 50, 10393–10399
Industrial & Engineering Chemistry Research ARTICLE

Table 2. Comparison of Calcium-Sulfate Inhibition

dosage, CaSO4 dosage of maximum CaSO4
inhibitor mg/L inhibition (%) threshold, mg/L inhibition (%)

AA
APEC 2 39 3 83
MA
APES 2 2 32 71
PAA 2 38 3 81
HPMA 2 79 2 79
PAPEMP 2 30 4 80

also calcium-sulfate scales at a low dosage, whereas MA
APES

only has ability to control calcium-phosphate scales and cannot
control calcium-sulfate scales at a low dosage. The data listed in
Table 2 also showed that, at their respective threshold dosage,
AA
APEC has the same calcium sulfate inhibition as PAA or
HPMA, the two most effective, commonly used nonphosphorus
inhibitors for calcium sulfate control. Furthermore, at a level of 2
mg/L, HPMA seemed more effective than AA
APEC for
calcium sulfate inhibition. However, the inability to inhibit
calcium-phosphate scales makes both PAA and HPMA less
desirable inhibitors. It is worth mentioning that, although the
performance of PAPEMP on calcium sulfate inhibition is equal to
that of PAA, HPMA, and AA
APEC at their threshold dosages,
PAPEMP does not have ability to control calcium-phosphate
scales until the dosage exceeds 30 mg/L, an unacceptable massive
dosage in industrial recycling water systems; these weaknesses
make PAPEMP a less desirable inhibitor.
The SEM images in Figure 6 show that regular rod-shaped
calcium sulfate tight particles were obtained in the absence of
inhibitor (Figure 6a), and loose calcium sulfate particles were
produced in the presence of AA
APEC (Figure 6b). It also
indicates that the use of only 2.5 mg/L AA
APEC had a Figure 6. SEM images of calcium sulfate crystals: (a) in the absence of
profound effect on the calcium sulfate crystal morphology inhibitor and (b) in the presence of 2.5 mg/L AA
APEC.
and size.
3.5. Inhibition Mechanism Toward Ca3(PO4)2, CaCO3, and embryos incorporate into the polymer matrix of AA
APEC, and
CaSO4 Scales. AA
APEC is a structurally well-defined biblock they are coated with double layers of PAA (inner layer) and PEG
copolymer, depicted in Figure 7a; one block is AA, and the other (outer layer). As a consequence, the aggregation of Ca3(PO4)2,
is APEC. The main chains are composed of allyl-terminated AA, CaCO3, and CaSO4 solid particles is blocked. In addition, the
denoted as PAA (marked with green ribbons in Figure 7), and the long PEG side chains in AA
APEC matrix result in steric and
side chains are made of carboxylate-capped polyethylene glycol electrostatic repulsion. Therefore, the existing minerals do not
(PEG) segments (marked with black ribbons in Figure 7). Both precipitate in the presence of AA
APEC through its excellent
PAA and PEG segments are hydrophilic blocks and exist ability to disperse solid particles such as calcium-phosphate
randomly in water (Figure 7b). When calcium ions are added scales. The fact that AA
APEC has excellent dispersancy activity
into AA
APEC solutions, carboxyl groups in AA
APEC ma- toward precipitation of calcium phosphate seems fit to TEM
trixes can recognize and encapsulate or react with positively images of calcium-phosphate crystals in Figure 3b, while it maybe
charged calcium ions either in solutions or on the surface of emphasizes that the copolymer of AA
APEC has superior ability
inorganic minerals, such as Ca3(PO4)2, CaCO3, and CaSO4.23
26 to inhibit the precipitation of calcium carbonate and calcium
Encapsulation or interaction, between calcium ions and carboxyl sulfate by the excellent solubility of AA
APEC
Ca complexes
groups, leads to the spontaneous formation of AA
APEC
Ca due to water-compatible PEG segments. It should be mentioned
complexes (Figure 7c). On the other hand, when negatively that the hypothesis of inhibition mechanism is consistent with
charged PO43
, SO42
, or CO32
ions are added into solutions, those of Antonia et al.,6 who reported that cationic polymers
the positively charged calcium ions also interact with these exhibited higher inhibitory performance resulting from the
negatively charged ions thereby forming Ca3(PO4)2, CaCO3, interactions between polycation (polymer) and polyanion
and CaSO4 crystal embryos. As a result, calcium ions acting as ties (silica). The study15 of Achilles et al. showed that the role of
simultaneously link AA
APEC through carboxyl groups and polycarboxylic acids as inhibitors of calcium-phosphate crystal
PO43
, SO42
, or CO32
ions through an electrostatic attractive growth was to bind calcium ions with polycarboxylates. However,
force. At the same time, water-compatible PEG segments,27
33 Ca cations formed high hydrophilic complexes originate from
that is to say, long side chains of AA
APEC, surrounding the inorganic minerals, such as Ca3(PO4)2, CaCO3, and CaSO4, as a
surfaces of Ca3(PO4)2, CaCO3, and CaSO4 crystal embryos, are result, structure matching between complexes and inorganic
stable toward aqueous phase because of their high hydrophilic minerals is an important factor during the process of inhibition.
properties (Figure 7b). Thus, Ca3(PO4)2, CaCO3, and CaSO4 For this reason, AA
APEC exhibited excellent Ca3(PO4)2 and
10397 dx.doi.org/10.1021/ie200051r |Ind. Eng. Chem. Res. 2011, 50, 10393–10399
Industrial & Engineering Chemistry Research ARTICLE

Figure 7. Encapsulation calcium ions route via carboxyl groups. (a) Structure of AA
APEC. (b) Random individual hydrophilic molecules of
AA
APEC in water (for simplicity reasons only six AA
APEC molecules are shown). (c) Formation of AA
APEC
Ca complexes arranged randomly.
(d) Solid particles surrounded by double layers of PAA (inner) and PEG (outer).

CaSO4 inhibition, while it exhibited only passable ability to ’ ACKNOWLEDGMENT

control CaCO3 deposits. We acknowledge National Nature Science Foundation of
China (50873026); Key Program for the Scientific Research
4. CONCLUSIONS Guiding Fund for Basic Scientific Research Operation Expendi-
ture of Southeast University (Grant 3207040103); Science and
(1) A nonphosphorus inhibitor, the copolymer of AA
APEC Technology Projects on Production, Teaching and Research,
was synthesized and exhibited 100% calcium phosphate Changzhou, Jiangsu Province of China (CV20090002); Support
inhibition at a level of 6 mg/L and 83% calcium sulfate Program for Training of 333 High-Level Talent, Jiangsu Province
inhibition at threshold dosage of 3 mg/L. AA
APEC also of China (BRA2010033); Additionally, Nature Science Fund of
displayed significant ability to control calcium-carbonate Jiangsu Province (BK2011692) is also appreciated.
scales in solutions, showing approximately 65% inhibition
whereas the popular nonphosphorus inhibitors of PAA,
HPMA, PESA, and T-225 exhibited only 20
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