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Relating Silica Scaling in Reverse Osmosis to Membrane Surface Properties

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DOI: 10.1021/acs.est.6b06411

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Relating Silica Scaling in Reverse Osmosis to Membrane Surface

Properties
Tiezheng Tong,‡,§,∥ Song Zhao,†,‡,∥ Chanhee Boo,‡ Sara M. Hashmi,‡ and Menachem Elimelech*,‡,§
†
School of Chemical Engineering and Technology, Tianjin Key Laboratory of Membrane Science and Desalination Technology,
Tianjin University, Tianjin 300072, P. R. China
‡
Department of Chemical and Environmental Engineering, Yale University, New Haven, Connecticut 06520-8286, United States
§
Nanosystems Engineering Research Center for Nanotechnology-Enabled Water Treatment (NEWT), Yale University, New Haven,
Connecticut, United States
*
S Supporting Information

ABSTRACT: We investigated the relationship between mem-

brane surface properties and silica scaling in reverse osmosis
(RO). The effects of membrane hydrophilicity, free energy for
heterogeneous nucleation, and surface charge on silica scaling
were examined by comparing thin-film composite polyamide
membranes grafted with a variety of polymers. Results show that
the rate of silica scaling was independent of both membrane
hydrophilicity and free energy for heterogeneous nucleation. In
contrast, membrane surface charge demonstrated a strong
correlation with the extent of silica scaling (R2 > 0.95, p <
0.001). Positively charged membranes significantly facilitated silica scaling, whereas a more negative membrane surface charge led
to reduced scaling. This observation suggests that deposition of negatively charged silica species on the membrane surface plays a
critical role in silica scale formation. Our findings provide fundamental insights into the mechanisms governing silica scaling in
reverse osmosis and highlight the potential of membrane surface modification as a strategy to reduce silica scaling.

■ INTRODUCTION
Silica is one of the most common inorganic scalants in
membrane desalination systems such as reverse osmosis (RO).
Silica is ubiquitous in natural waters, with concentrations
normally in the range of 1−60 mg/L.1−3 Once feedwater silica
concentration exceeds its solubility limit (typically 100−150
mg/L at near neutral pH2,4,5), insoluble silica precipitates and
forms scale on the membrane surface. Silica scaling causes
severe flux decline and requires chemical and mechanical
cleaning operations,2−4,6,7 which limits the efficiency and water
recovery of RO desalination. In particular, silica scaling is a
major barrier for efficient operation of inland brackish water
RO desalination where high water recovery is critical for brine
management.4,6,8
The chemistry and mechanisms of silica scaling are complex
and not well understood.4 Silica scaling involves the polymer-
ization of monomeric silicic acids forming Si−O−Si bonds via
dehydration.4,9 Polymerization of the weakly acid silicic acids
produces various silica species ranging from dimers and trimers
to polymers and particles.10 Although heterogeneous nuclea-
tion, in which silicic acids deposit and polymerize on the
membrane surface, has been proposed as the major mechanism
of silica scaling,2,11 bulk deposition of colloidal silica may also
play an important role.4,7
Current strategies for silica scaling control in membrane
desalination rely heavily on the use of scale inhibitors (or
antiscalants). Scale inhibitors stabilize silica species in solution
and subsequently prevent the formation of scale on the
membrane surface.12−14 However, the use of scale inhibitors
increases the operation cost of desalination and can result in
organic and biological fouling.15,16 Since the solubility of silica
increases with pH, high operation pH (i.e., pH > 10) has been
used as an alternative strategy to scale inhibitor addition in RO
desalination of silica-rich feedwater at high water recov-
eries,17,18 but high operation pH leads to the precipitation of
calcium and magnesium silicates.19 As a result, extensive
pretreatments, such as chemical softening and cationic
exchange, are required to remove hardness from the feed-
water.20 Therefore, silica scaling remains a challenging problem
facing membrane desalination, making development of new
strategies for scaling control highly desired.
Membrane surface modification may be a promising
approach to reduce silica scaling. Previous studies have
demonstrated that surface chemistry influences silica scaling.
For example, by using an organic silica precursor, Wallace et
al.21 have shown that silica nucleation occurred on model
surfaces with carboxyl or hybrid amine/carboxyl functional
groups but not on amine-terminated surfaces. When compared
to a cellulose acetate membrane with surface hydroxyl groups,
Received: December 17, 2016
Revised: February 20, 2017
Accepted: March 28, 2017
Published: March 28, 2017

© 2017 American Chemical Society 4396 DOI: 10.1021/acs.est.6b06411

Environ. Sci. Technol. 2017, 51, 4396−4406
Environmental Science & Technology Article

Figure 1. Schematics of membrane modification approaches. Activators regenerated by electron transfer−atom transfer radical polymerization
(ARGET-ATRP) was employed to graft poly(acrylamide) (PAM), poly(sulfobetaine methacrylate) (PSBMA), and poly([2-(methacryloyloxy)-
ethyl]trimethylammonium chloride) (PMTAC) on the membrane surface, assisted by dopamine-bromoisobutyryl bromide (Bibb) as the initiator.
Redox radical initiation was employed to graft poly(acrylic acid) (PAA) on the membrane surface. Direct grafting, assisted by dopamine, was
employed to graft polyethylenimine (PEI) and 1H,1H,2H,2H-perfluorodecanethiol (PFDT) on the membrane surface. For PEI, two molecular
weights were used, 800 and 1300 g/mol.

polyamide membranes with native carboxyl groups showed

more irreversible silica scaling in both RO and forward osmosis
operation.2
To date, membrane surface modification has been used
extensively for reducing organic and biological fouling in
membrane desalination systems.22−28 In contrast, very few
studies have focused on surface modification for inorganic
scaling control. For example, a hydrophilic brush layer of
poly(methacrylic acid) or poly(acrylamide) was shown to
mitigate gypsum scaling on polyamide RO membranes.29,30
These brush layers provided effective screening of the
underlying membrane surface, and their partial local motility
reduced the attachment rate of gypsum nuclei and/or
crystallites.29,30 To the best of our knowledge, however,
applications of membrane surface modification in reducing
silica scaling have not been reported in the literature.
Elucidating how membrane surface properties influence silica
scaling is the prerequisite for developing scaling-resistant
membrane surfaces.
In this work, we investigated the relationship between
membrane surface properties and silica scaling in reverse
osmosis. A commercial thin-film composite (TFC) polyamide
membrane was modified with diverse polymer coatings, which
provided different surface hydrophilicity, free energy for
heterogeneous nucleation, and surface charge. The performance
of the modified membranes with a silica-saturated feed solution
was tested in a bench-scale cross-flow RO system. The water
flux decline rate obtained from the scaling experiments was
used to examine the effect of membrane surface properties on
the extent of silica scaling. We demonstrate that membrane
surface chemistry significantly influences silica scaling, with
membrane surface charge identified as the primary regulating
factor. Our findings promote a mechanistic understanding of
silica scaling of RO membranes, which may guide the design
and development of effective scaling-resistant membranes.
4397
■ MATERIALS AND METHODS
Materials and Chemicals. Acrylamide (>99.0%), [2-
(methacryloyloxy)ethyl]dimethyl-(3-sulfopropyl)ammonium
hydroxide (also known as sulfobetaine methacrylate, SBMA),
[2-(methacryloyloxy)ethyl]trimethylammonium chloride solu-
tion (MTAC, 80 wt % in H2O), polyethylenimine (PEI,
branched, Mw of ∼800 g/mol and ∼1300 g/mol),
1H,1H,2H,2H-perfluorodecanethiol (PFDT, 97%), acrylic acid
(99%), N,N-dimethylformamide (DMF), triethylamine (TEA,
≥99%), α-bromoisobutyryl bromide (BiBB, 98%), dopamine
hydrochloride, copper(II) chloride (99%), copper(II) bromide
(99%), tris(2-pyridylmethyl)amine (TPMA), L-ascorbic acid,
potassium persulfate (K2S2O8, ≥99%), sodium metabisulfite
(Na2S2O5, ≥99%), and sodium metasilicate pentahydrate
(Na2SiO3·5H2O, >95.0%) were purchased from Sigma-Aldrich.
Calcium chloride dihydrate (CaCl2·2H2O) and magnesium
chloride hexahydrate (MgCl2·6H2O) were purchased from Alfa
Aesar and J.T. Baker, respectively. Commercial TFC RO
membranes (SW30 XLE) were provided by Dow Chemical.
Deionized (DI) water was obtained from a Milli-Q ultrapure
water purification system (Millipore).
Membrane Surface Modification Approaches. Com-
mercial RO membranes were immersed in 25% isopropyl
alcohol for 30 min, after which the membranes were washed
thoroughly with DI water and stored at 4 °C until use. Three
modification approaches were employed to tailor the surface
chemistry of RO membranes with various polymer coatings: (i)
activators regenerated by electron transfer−atom transfer
radical polymerization (ARGET-ATRP), (ii) redox radical
initiation, and (iii) dopamine-assisted direct grafting (Figure 1).
The selected polymers (as described below) have different
functional groups, creating diverse membrane surface proper-
ties in terms of surface hydrophilicity, free energy for
heterogeneous nucleation, and surface charge.
ARGET-ATRP is a robust and versatile approach to produce
polymer brushes with narrow polydispersity and controllable
DOI: 10.1021/acs.est.6b06411
Environ. Sci. Technol. 2017, 51, 4396−4406
Environmental Science & Technology
thickness and architecture.31,32 This approach, performed
following literature protocols with slight modification,31,33 was
used for grafting poly(acrylamide) (PAM), poly(sulfobetaine
methacrylate) (PSBMA), and poly([2-(methacryloyloxy)ethyl]-
trimethylammonium chloride) (PMTAC) on the membrane
surface.
Briefly, dopamine hydrochloride (400 mg, ∼2.10 mmol) was
dissolved in 20 mL of DMF in an amber bottle with a PTFE/
red rubber septum, followed by adding TEA (0.15 mL, 1.05
mmol) and Bibb (0.13 mL, 1.05 mmol). After 3 h of stirring
under N2 at room temperature, the mixture containing
dopamine-Bibb was added to 100 mL of aqueous tris-
(hydroxymethyl)aminomethane buffer (pH 8.5), which was
then immediately poured onto the membrane active layer.
Dopamine-Bibb self-polymerized and formed poly(dopamine-
Bibb) (PDA-Bibb) on the membrane surface, which served as
the initiator for polymer growth. After 3 h, the PDA-Bibb
deposited membrane was thoroughly rinsed with DI water.
Acrylamide (14.2 g, ∼0.2 mol), SBMA (15.64 g, ∼56 mmol), or
MTAC (14.52 g, ∼56 mmol) monomers were dissolved in 200
mL of 1:1 isopropyl alcohol:DI water mixture (v/v) in a bottle
with a septa lid (covered with aluminum foil). After degassing
with N2 for 10 min, the PDA-Bibb deposited membrane was
placed into the bottle. After another 10 min degassing with N2,
a solution of copper(II) salt and TPMA in an 8 mL 1:1
isopropyl alcohol:DI water mixture (v/v) was injected into the
bottle. Cu(II) bromide (0.008 g, ∼35.8 μmol) and TPMA
(0.065 g, ∼0.225 mmol) were used for grafting PAM, whereas
Cu(II) chloride (0.004 g, ∼29.8 μmol) and TPMA (0.056 g,
∼0.193 mmol) were used for grafting PSBMA and PMTAC.
After an additional 10 min degassing with N2, 8 mL of ascorbic
acid (0.8 g, ∼4.5 mmol) in a 1:1 isopropyl alcohol:DI water
mixture (v/v) was injected into the bottle to initiate the
polymerization. The reaction lasted for 1 h, 3 d, and 7 d for
PSBMA, PMTAC, and PAM, respectively. The longer
polymerization duration for PMTAC and PAM was due to
their slower polymerization rate than SBMA. Finally, the bottle
was opened to air to terminate the reaction. The modified
membranes were washed thoroughly with DI water and stored
at 4 °C until use.
Redox radical initiation was used to create poly(acrylic acid)
(PAA)-modified membranes, following the protocol reported
by Belfer et al.34 In this approach, oxygen-centered radicals
formed by the action of redox initiators (i.e., K2S2O8 and
Na 2 S 2O 5) are effective to graft vinyl monomers with
subsequent polymerization.34 In brief, 1 M solution of acrylic
acid was prepared, followed by adding 0.01 M K2S2O8 and 0.01
M Na2S2O5 to the monomer solution. The mixture was then
immediately poured onto the membrane active layer. After 1 h,
the PAA-modified membrane was rinsed thoroughly with DI
water and stored at 4 °C until use.
Dopamine-assisted direct grafting modification was used to
create PEI- and PFDT-modified membranes. The catechol
groups of polydopamine (PDA) (after oxidation to quinone)
react with amine or thiol groups of the polymers through the
Michael-type addition or Schiff base reaction,35−37 thereby
grafting the polymers directly onto the membrane surface. In
brief, dopamine hydrochloride (30 mg, ∼0.157 mmol) was
dissolved in 30 mL of tris(hydroxymethyl) aminomethane
buffer (10 mM, pH 8.5). The mixed solution was then poured
onto the membrane active layer. Dopamine polymerization to
PDA lasted for 1 h at room temperature. After rinsing with DI
water, the PDA-deposited membrane was immersed in 10 g/L
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PEI aqueous solution or 0.05% (v/v) PFDT ethanol:DI water
solution (1:1, v/v) for 4 h at room temperature. After the
reaction, the solution was removed, and the PEI- or PFDT-
modified membrane was rinsed thoroughly with DI water and
stored at 4 °C until use.
Membrane Surface Characterization. Membrane surface
morphology was investigated by scanning electron microscopy
(SEM, Hitachi SU-70). Before taking the images, membrane
samples were dried and sputter-coated with a thin layer of
chromium or iridium. Membrane surface roughness was
evaluated by atomic force microscopy (AFM, Bruker
Dimension Fastscan) in tapping mode with a silicon nitride
probe (ScanAsyst-air, Burker). Micrographs were captured
from six different locations with an area of 10 μm × 10 μm.
Attenuated total reflectance-Fourier transform infrared (ATR-
FTIR) spectra were collected using a Thermo Nicolet 6700
spectrometer with 32 scans for each sample. Membrane surface
hydrophilicity was analyzed by measuring the water contact
angle using the sessile drop method.38 The zeta potential of the
membrane surface was determined using a streaming potential
analyzer with an asymmetric clamping cell (EKA, Brookhaven
Instruments). The measurements were conducted with a
solution containing 1 mM KCl and 0.1 mM KHCO3. Details
on the procedure used to calculate the zeta potential from the
measured streaming potential are described elsewhere.39
Free Energy for Heterogeneous Silica Nucleation. The
thermodynamic barrier to silica nucleation is determined by the
free energy of forming a silica nucleus of a critical size
(ΔGcri).40 Because the membrane surface promotes nucleation,
the critical free energy for heterogeneous nucleation (ΔGhet
cri ) is
smaller than that for homogeneous nucleation (ΔGhom cri ). The
critical free energy for heterogeneous nucleation can be
calculated from21,40,41
het hom
ΔGcri = f (θ )ΔGcri (1)
(2 + cos θ )(1 − cos θ )2
f (θ ) =
4 (2)
The correction factor f(θ), or the wetting function, describes
the geometry of the nucleus-surface interaction (Figure S1).21
The value of f(θ) ranges from zero to one and is a function of
the contact angle (θ) between the silica nucleus and the
membrane surface. θ is calculated using Young’s equation that
involves the interfacial free energy among silica, water, and the
membrane surface41
γmem − wat − γmem − SiO
2
cos θ =
γSiO − wat (3)
2
where γmem−wat, γmem−SiO2, and γSiO2−wat denote the interfacial
free energies associated with the membrane−water, mem-
brane−silica, and silica−water boundaries at thermodynamic
equilibrium, respectively.
Since ΔGhom
cri for silica is constant at a fixed temperature and
saturation index (eq S1 in the Supporting Information), ΔGhet cri
is proportional to the value of f(θ), which is a characteristic
property of the membrane surface. The value of f(θ) was
calculated for each membrane, with a larger f(θ) corresponding
to a higher thermodynamic barrier (or lower membrane scaling
propensity) to heterogeneous silica nucleation. The procedure
for calculating f(θ), γmem−wat, γmem−SiO2, and γSiO2−wat is detailed
DOI: 10.1021/acs.est.6b06411
Environ. Sci. Technol. 2017, 51, 4396−4406
Environmental Science & Technology
Figure 2. (A) Water contact angle, (B) zeta potential, and (C) water permeability coefficient (A), salt permeability coefficient (B), and salt rejection
of the different membranes analyzed in this study. The full names of PAM, PSBMA, PMTAC, PEI, PFDT, PAA, and Bibb have been defined in
Figure 1 and in the main text. PDA and PDA-Bibb stand for dopamine and dopamine-Bibb after polymerization, respectively. The error bars
represent standard deviation and were calculated from eight (for zeta potential) and duplicate (for A, B, and salt rejection) measurements.
in the Supporting Information, following methods and
equations described in the literature.23,40,42
Measurement of Membrane Transport Properties.
The transport properties of the membranes were determined
using a bench-scale crossflow RO system. Details of the
experimental setup have been described in our previous
work.43,44 The membrane coupon (with an effective area of
20.02 cm2) was compacted overnight using DI water under a
pressure of 31.0 bar (450 psi). The water permeability
coefficient (A) was calculated from the pure water flux
measured under 27.6 bar (400 psi) at 22 ± 1 °C. The salt
permeability coefficient (B) was calculated from the salt
rejection measured under 27.6 bar (400 psi) at 22 ± 1 °C
with 50 mM NaCl as the feed solution and a cross-flow velocity
of 21.3 cm/s.45
RO Membrane Silica Scaling Tests. Scaling tests with the
various membranes were conducted using a bench-scale RO
system and a silica-saturated feed solution. The configuration of
the RO system was identical to that used in measuring the
membrane transport properties.43,44
The silica-saturated feed solution was composed of 2.8 mM
Na2SiO3·5H2O, 7.0 mM CaCl2, 3.5 mM MgCl2, and 35 mM
NaCl, simulating brackish groundwater after 70−80% recov-
ery.46 A solution containing Na2SiO3·5H2O and NaCl was
prepared first with the pH of ∼11. Then, CaCl2 and MgCl2
were added after the pH was adjusted to less than 7 in order to
avoid precipitation of calcium and magnesium silicate salts.13,47
The pH was further adjusted to 6.50 ± 0.05. Thermodynamic
calculations using PHREEQC48 and the database MINTEQ
(version 4) showed that silica was the only precipitate formed
in the feed solution, with a saturation index (defined as the ratio
of the ion activity product to the solubility product) of 1.5 for
amorphous silica.
Prior to silica scaling, membranes were compacted overnight
using DI water under 31.0 bar (450 psi), after which pure water
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flux of the membrane was recorded under 27.6 bar (400 psi) at
a crossflow velocity of 8.5 cm/s. Then, the silica scaling
experiment was initiated by adding the silica-saturated solution
to the RO feed reservoir. The applied pressure (27.6 ± 2.8 bar)
was adjusted to create an initial water flux of 56 ± 2 L m−2 h−1.
The water flux was continuously monitored for 1400 min at a
constant crossflow velocity of 8.5 cm/s. A recycling mode was
employed, with the permeate recycled back to the feed solution.
The feed solution temperature during the silica scaling tests was
maintained constant at 22 ± 1 °C.
After silica scaling, membrane cleaning was performed by
rinsing the membrane with DI water at a high crossflow velocity
of 21.3 cm/s for 30 min. After the cleaning step, pure water flux
of the membrane was measured at 27.6 bar (400 psi) and a
crossflow velocity of 8.5 cm/s to determine the flux recovery
ratio. The membranes before and after silica scaling were
analyzed by SEM, energy-dispersive X-ray (EDX) spectroscopy,
and ATR-FTIR spectroscopy, to examine the morphology and
chemical composition of silica scale formed on the membrane
surface.
■ RESULTS AND DISCUSSION
Modified Membranes Exhibit Diverse Surface Proper-
ties. The membranes tested in this study were analyzed by a
combination of different techniques to characterize key surface
properties, namely membrane morphology, surface function-
ality, surface hydrophilicity, and surface charge.
SEM was employed to observe the morphology of membrane
surfaces (Figure S2). Except for the membrane grafted with PEI
of 1300 g/mol (PEI-1300), all modified membranes exhibited a
ridge-and-valley surface structure similar to the control
commercial RO membrane, indicating that the polymer films
formed on the membrane surfaces were ultrathin. The surface
roughness of each membrane was further quantified by AFM
(Figure S3). Results show that surface modification did not
DOI: 10.1021/acs.est.6b06411
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change the membrane surface roughness. The lack of alteration
in surface roughness after modification by PEI-1300 was likely
due to the low thickness of the polymer layer relative to the
surface roughness of the unmodified (control) membrane.
Membrane surface functionality was characterized by ATR-
FTIR spectroscopy. As shown in Figure S4, ATR-FTIR spectra
of the tested membranes represented a combination of spectra
from both the polyamide active layer and the polysulfone
support layer. For example, the absorbance at ∼1670 cm−1 and
∼1540 cm−1 corresponds to N−CO and C−N−H vibrations
of the amide groups,34 while the peak at 1294 cm−1 originates
from the SO stretching in polysulfone.31 A new peak was
observed at 1726 cm−1 for both PSBMA- and PMTAC-
modified membranes, which is attributed to the carbonyl in the
ester group of SBMA and MTAC molecules.31 The PSBMA-
modified membrane also showed an additional peak at 1039
cm−1 that arises from the symmetric stretch of sulfonate group
in SBMA.31 Although native carboxyl groups are present in the
polyamide active layer due to the hydrolysis of unreacted acyl
chloride groups,49 their density (approximately 1−30 charges
nm−250) was too low to be detected by ATR-FTIR for the
unmodified control membrane.34 The PAA-modified mem-
brane exhibited an increased signal at ∼1720 cm−1 due to C
O stretching,51,52 suggesting an increase of carboxyl group
density on the membrane surface. For the other modified
membranes, the characteristic peaks of the grafted polymers
overlapped with those of the TFC polyamide membrane.
Therefore, no difference in the ATR-FTIR spectra was
observed as compared to the control membrane.
Membrane surface hydrophilicity was determined by
measuring the water contact angle of each membrane. As
shown in Figure 2A, the control membrane was relatively
hydrophilic with a water contact angle of ∼30°, which was
lower than reported values for pristine TFC polyamide
membranes (>50°38,53). We attribute this result to proprietary
polymer coating on the commercial membrane surface.54 After
modification with PAM, PSBMA, PEI, and PAA polymers, the
membrane surface became more hydrophilic, with water
contact angles lower than 20°. The reduction in water contact
angle was attributed to the introduction of polar functional
groups (−OC−NH2, −NH2/−NH, and −COO− for PAM,
PEI, and PAA, respectively) or zwitterionic brush layer (for
SBMA), which increased the affinity of water molecules to the
membrane surface.55−57 Conversely, grafting of the PFDT
polymer created a more hydrophobic surface (water contact
angle >110°) due to the abundance of fluorine groups.36 In
addition, membrane modifications with PMTAC, PDA, and
PDA-Bibb resulted in a slight, but statistically insignificant,
increase of membrane hydrophilicity as compared to the
control membrane.
Zeta potential indicates the surface charge properties of the
membrane,39 which may impact the adsorption of charged
foulants due to electrostatic interactions. The zeta potential of
each membrane was calculated from streaming potential
measurements as a function of pH.39 As shown in Figure 2B,
the control membrane had negative surface charge over the
range of investigated solution pH (i.e., pH of 3−9). The
negative surface charge is attributed to the deprotonation of
carboxylic groups formed in the interfacial polymerization
process.58
Membrane surface modification with different polymers
altered the membrane zeta potential, providing additional
evidence for the success of polymer grafting. PMTAC and PEI
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increased the membrane zeta potential dramatically, with the
membrane surface charge shifting from negative to positive at
almost every investigated solution pH. The positive charge was
derived from the quaternary ammonium of MTAC31,59 or
abundant amine groups of PEI molecules.60,61 In contrast, the
PAA-modified membrane exhibited a more negatively charged
surface than the control membrane, consistent with its higher
surface density of carboxyl groups as revealed by ATR-FTIR
spectra. The other polymers used in this study generally
diminished the negative surface charge as compared to the
unmodified control membrane. For example, the zeta potential
at near neutral pH changed from ∼−12 mV for the control
membrane to ∼−6 mV for the PSBMA- and PAM-modified
membranes. The grafting of these net zero charge polymers
covered the underlying negatively charged functional
groups.29,31
Membrane Transport Properties. As shown in Figure
2C, most modified membranes exhibited slightly higher water
permeability coefficients (A between 2.6 ± 0.0 and 3.0 ± 0.2 L
m−1 h−1 bar−1) than the control membrane (A of 2.5 ± 0.0 L
m−1 h−1 bar−1), probably due to their improved membrane
hydrophilicity. However, both PEI-modified membranes
showed reduced water permeability (2.3 ± 0.1 L m−1 h−1
bar−1). We noticed that the grafting of hydrophobic PFDT
polymer did not decrease membrane water permeability. This
counterintuitive phenomenon was attributed to the use of
ethanol to dissolve PFDT during the membrane modification
process. Ethanol could swell the polyamide active layer by
enhancing chain flexibility and chain−chain distance, resulting
in a larger free volume that facilitates water transport.62 After
immersing the control membrane in 1:1 ethanol:DI water
solution for 4 h, the membrane water permeability increased by
40% and became significantly higher than that of the PFDT-
modified membrane (Figure S5).
Salt permeability coefficients (B) of the membranes were
calculated from the measured water flux and salt rejection after
accounting for concentration polarization (Figure 2C).45 The
average salt rejection of the control membrane was 99.0% with
50 mM NaCl in the feed solution, while the modified
membranes exhibited similar or slightly lower salt rejection of
98.4%−99.1%. Except for the membrane modified with PEI-
1300, the calculated salt permeability coefficients moderately
increased after membrane modification, reflecting the water
permeability−salt permeability trade-off of TFC polyamide
membranes.63 Therefore, the intrinsic membrane transport
properties were not greatly affected by surface modification in
our study.
Membrane Surface Modification Influences Silica
Scaling. The silica scaling tests were conducted with a silica-
saturated feed solution (saturation index of 1.5) in a bench-
scale cross-flow RO system. As shown in Figure S6A, the water
flux of the control membrane decreased gradually with a total
flux decline of ∼15% after 1400 min. No flux recovery was
achieved after membrane cleaning (Figure S6B), consistent
with our previous finding that silica scaling of polyamide
membranes in RO mode was irreversible.2 SEM images
revealed that the scaled membrane surface was fully covered
by a layer of particles (Figures S6C and S7), with the ridge-and-
valley surface structure no longer visible. EDX spectra clearly
showed the energy peak of Si at 1.74 keV (Figure S6C); no
signal of Ca or Mg was detected, thus excluding the formation
of calcium and magnesium scale. Compared to the pristine
membrane, increased signals associated with Si−OH (1654
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Figure 3. Results of silica scaling tests for the different membranes analyzed in this study (definition of each membrane was given in Figure 1). (A)
Representative water flux decline curve of each membrane. (B) Normalized water flux after scaling and after rinsing. The silica scaling tests were
conducted with an initial water flux of 56 ± 2 L m−2 h−1 and a cross-flow velocity of 8.5 cm/s for 1400 min at a temperature of 22 ± 1 °C. The
composition of feed solution included 2.8 mM Na2SiO3, 7 mM CaCl2, 3.5 mM MgCl2, 35 mM NaCl, and pH = 6.50 ± 0.05. The saturation index of
amorphous silica was 1.5 as calculated by PHREEQC and the thermodynamic database MINTEQ (Version 4). The error bars in part B represent
standard deviation and were calculated from triplicate measurements.

Figure 4. Relating the extent of silica scaling (expressed as water flux decline ratio) to (A) membrane water contact angle and (B) free energy for
heterogeneous nucleation (expressed as the wetting function f(θ)). Water flux decline ratio is defined as the percentage of flux decline as compared
to the initial water flux. The value of f(θ) was calculated as described in the Materials and Methods section and the Supporting Information. The
error bars represent standard deviation and were calculated from at least five (for water contact angle) and triplicate (for water flux decline ratio)
measurements. The calculation of f(θ) values involves the average contact angles in water, glycerol, and diiodomethane, as well as the average surface
roughness of the membranes.

cm−1)64 and Si−O−Si bonds (between 1050 and 1100
cm−1)65,66 were detected in the ATR-FTIR spectra after
membrane scaling (Figure S6D). These analyses unambigu-
ously confirmed the formation of silica scale on the membrane
surface.
Water flux decline curves of all modified membranes were
compared with that of the control membrane (Figure 3A). RO
membranes modified with different polymers showed varied
extents of flux decline due to silica scaling. Since other factors
potentially influencing the rate of silica scaling (e.g., permeate
flux, trans-membrane pressure, cross-flow velocity, and feed-
water chemistry) were kept the same during the scaling tests for
all membranes, the observed variation in water flux decline is
attributed to the difference in membrane surface properties.
Membranes modified with PMTAC and two PEI polymers
experienced the most severe flux decline (∼30% after 1400
min), significantly higher than that for the control membrane
(∼15%, p < 0.015 in paired t test). In contrast, the PAA-
modified membrane showed the lowest flux decline (∼12%).
All other modified membranes displayed a larger water flux
decline than the control membrane, suggesting that the grafted
polymer layers favored silica scale formation. In addition, except
for the PAA-modified membrane, no recovery of water flux was
4401
observed for all other modified membranes after membrane
cleaning (Figure 3B), underscoring the irreversibility of silica
scaling in RO operation.
Silica scaling on the membrane surface is governed by both
silica−membrane and silica−silica interactions.2 The membrane
surface was directly exposed to silica scalants at the initial stage
of the scaling tests, when membrane surface properties
influenced silica deposition and nucleation by controlling
silica−membrane interactions. However, the influence of
membrane surface properties diminished as the membrane
surface was progressively covered by a silica layer, after which
further accumulation of silica scale was controlled by silica−
silica interactions. This transition was notably observed for the
MTAC- and PEI-modified membranes that have high scaling
propensity. Specifically, these membranes experienced a rapid
flux decline at the beginning of the scaling tests, reducing the
water flux by more than 10% within 6 h. The flux decline rate
was then decelerated and became comparable to the other
membranes after ∼800 min, indicating that the membrane
surfaces were covered by silica scale. In contrast, the PAA-
modified membrane maintained 99% of the initial water flux
during the first 6 h, suggesting that the initial deposition of
DOI: 10.1021/acs.est.6b06411
Environ. Sci. Technol. 2017, 51, 4396−4406
Environmental Science & Technology
Table 1. Interfacial Free Energies and Wetting Function of the Different Membranes Analyzed in This Study
membrane control PAM PSBMA PMTAC
γmem−wata −1.73 −6.64 −4.70 −2.60
γmem−SiO2a 1.75 1.23 1.20 1.20
γSiO2−wata −8.84 −8.84 −8.84 −8.84
f(θ)b 0.22 0.009 0.074 0.197
a
γmem−wat, γmem−SiO2, and γSiO2−wat represent the interfacial free energies between membrane surface and water, membrane surface and silica, and silica
and water, respectively (in mJ/m2). bf(θ) is the wetting function that is proportional to the free energy for heterogeneous nucleation. The procedure
of calculating these parameters is detailed in the Materials and Methods section as well as the Supporting Information.
silica species on the membrane surface was effectively reduced
with PAA polymers.
Silica Scaling Is Independent of Membrane Hydro-
philicity and Free Energy for Heterogeneous Nuclea-
tion. In order to delineate the relationship between membrane
hydrophilicity and silica scaling, the water flux decline ratio of
each membrane was plotted against the corresponding water
contact angle (Figure 4A). No correlation was observed (R2 =
0.03, p = 0.61), indicating that silica scaling is independent of
membrane hydrophilicity. For example, although membranes
modified with PFDT, PDA, and PSBMA exhibited distinct
water contact angles (119 ± 7°, 26 ± 3°, and <10°, respectively,
Figure 2A), they displayed comparable water flux decline ratios
(∼20%) after 1400 min scaling tests.
An increase in membrane hydrophilicity generally improves
membrane resistance to organic and biological fouling.22,67 A
strong hydration layer formed on hydrophilic surfaces
effectively reduces adsorption of both organic and biological
foulants (e.g., organic macromolecules,23,38 proteins,23,31,68 and
bacterial cells31). However, this strategy was ineffective in
reducing silica scaling in our study. In fact, modified
membranes with improved hydrophilicity experienced a larger
water flux decline than the unmodified control membrane in
most cases (except for the PAA-modified membrane). Unlike
organic and biological foulants, the small silicic acid molecules
can diffuse through the hydration layer and grafted polymer
films. Due to their abundant silanol groups, silicic acid
molecules or other silica species can form strong hydrogen
bonding with the grafted polymer and polyamide surface,
subsequently initiating the formation of silica nuclei. Our
hypothesis is further supported by a recent study in which
hydrogen bonding between silanol groups and hydrophilic
polyethylene glycol polymers was observed in aqueous
solution.69 Therefore, despite the presence of a bound
hydration layer, silicic acids could still reach the membrane
surface, polymerizing and forming silica scale on the hydro-
philic polymer brushes and/or the underlying polyamide active
layer.
The wetting function, f(θ), was calculated as a proxy to
estimate the energy barrier to heterogeneous silica nucleation
on each membrane surface.21,40 As shown in Table 1, the
membranes tested in this study showed different values of f(θ),
which correspond to varied membrane susceptibility to silica
nucleation. The highly hydrophilic membranes (e.g., the PAM-,
PSBMA-, and PEI-modified membranes) exhibited lower f(θ)
values than the unmodified control membrane, suggesting that
silica nucleation is more likely to occur on the hydrophilic
membranes. In contrast, the hydrophobic PFDT-modified
membrane showed the largest f(θ) value (close to 1), for
which heterogeneous silica nucleation is thermodynamically
unfavorable.
Article
PEI-800 PEI-1300 PFDT PAA PDA PDA-Bibb
−5.74 −6.71 31.96 −3.59 0.15 −0.88
1.44 0.96 24.56 1.29 0.44 0.15
−8.84 −8.84 −8.84 −8.84 −8.84 −8.84
0.025 0.012 0.98 0.128 0.47 0.33
The calculated f(θ) values, however, were not correlated to
the water flux decline caused by silica scaling (R2 = 0.07, p =
0.46, Figure 4B). For example, silica nucleation proceeds
against a higher energy barrier on the PMTAC-modified
membrane (f(θ) = 0.197) than the PAM- and PSBMA-
modified membranes ( f(θ) < 0.1). Although silica nucleation
was less likely to occur on the PMTAC-modified membrane, a
more severe water flux decline was observed on that membrane
than on the other two membranes (Figure 3). The PAA-
modified membrane, which showed the least extent of silica
scaling, had a lower f(θ) value than the control membrane. In
addition, the PFDT-modified membrane with the highest
thermodynamic barrier to silica nucleation experienced a larger
flux decline as compared to the control and PAA-modified
membranes.
Our results suggest that although heterogeneous nucleation
plays a significant role in silica scaling of TFC polyamide
membranes,2,11 the thermodynamic barrier to heterogeneous
silica nucleation does not predict the rate of silica scaling on
RO membranes. It is likely that heterogeneous nucleation is
influenced by both thermodynamic and kinetic factors. A study
by Wallace et al.21 reported that kinetic drivers were the
dominating factor in regulating silica nucleation on self-
assembled monolayers. The kinetic variability of silica
nucleation could arise from varied rates of silicic acid
attachment and different surface concentrations of ionized
silicic acid species.21 As a result, the rate of silica scaling can be
significantly enhanced without reducing the energy barrier to
heterogeneous nucleation. The impact of membrane surface
chemistry on the kinetics of silica nucleation will be discussed
in more detail in the following subsection.
Deposition of colloidal silica from bulk solution (homoge-
neous nucleation) could also contribute to silica scaling.
Dynamic light scattering (DLS) was performed to investigate
particle formation in the feedwater for the silica scaling tests
(detailed procedure of DLS measurements is provided in the
Supporting Information). Although a negligible amount of silica
particles was detectable in the feedwater within 24 h, formation
of colloidal silica particles was clearly evident when considering
concentration polarization (Figure S8). The presence of silica
particles near the membrane surface could cause water flux
decline by direct deposition, causing the scaling results to
deviate from those predicted by heterogeneous nucleation
theory.
Silica Scaling Is Strongly Dependent on Membrane
Surface Charge. As shown in Figure 5, silica scaling exhibited
a strong and statistically significant correlation with membrane
surface charge at near neutral pH (R2 = 0.958, p < 0.001).
Membranes with a more positive surface charge exhibited a
higher water flux decline due to silica scaling, whereas an
increase of negative surface charge reduced silica scaling. The
4402 DOI: 10.1021/acs.est.6b06411
Environ. Sci. Technol. 2017, 51, 4396−4406
Environmental Science & Technology
Figure 5. Relating the extent of silica scaling expressed as water flux
decline ratio to membrane surface charge characteristics quantified by
zeta potential at pH 6. The data were fitted by linear regression, which
showed a strong and statistically significant correlation (R2 > 0.95, p <
0.001) between membrane surface charge and water flux decline ratio.
The error bars represent standard deviation and were calculated from
eight (for zeta potential) and triplicate (for water flux decline ratio)
measurements. Similar correlation was observed when using zeta
potential at pH 7 (Figure S9 in the Supporting Information). Note
that our silica scaling experiments were carried out at pH 6.5.
PEI- and MTAC-modified membranes, which have positive
zeta potentials at near neutral pH (Figure 2B), experienced the
largest water flux decline in the scaling test (Figure 3). In
contrast, the PAA-modified membrane with the most negatively
charged surface showed the lowest susceptibility to silica
scaling. The other modified membranes exhibited a higher
extent of silica scaling than the control membrane, which was in
accordance with their less negative surface charge.
Proposed Mechanism for Silica Scaling. Polymerization
of silicic acids on the membrane surface, which has been
considered the major mechanism of silica scaling on TFC
polyamide membranes,2,11 is mainly driven by the reaction
between ionized and neutral silicic acid molecules.9,70−72
Compared with their neutral counterparts, the ionized silicic
acids (with negative charges) react more readily with other
silicic acid molecules.73 The high reactivity of ionized silicic
acids is probably due to the formation of Si−O bonds between
the deprotonated silanol groups and the Si center of silicic acid
molecules.74 As polymerization of silicic acids proceeds, silica
species tend to have a higher density of ionized silanol groups,
Figure 6. Schematic of proposed mechanism for the role of membrane surface charge in silica scaling. For a positively charged membrane surface, the
negatively charged silica species are attracted to the membrane surface, causing severe decline in water flux. In contrast, a negatively charged
membrane surface repels silica species, resulting in reduced water flux decline during silica scaling. Note that the negatively charged silica species not
only represent monomers and dimmers but also include other silica species such as trimers, oligomers, and polymers.
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Article
due to the lower pKa value of silica oligomers (pKa of ∼6.8)
compared to monomeric silicic acids (pKa of ∼9.8).75 Similar to
ionized silicic acid, the resultant ionized silica species are very
reactive, and other silica species react preferentially with those
negatively charged species.75
The negatively charged ionized silica species play a critical
role in the kinetics of silica polymerization, which explains our
observed RO membrane scaling results. As illustrated in Figure
6, a positively charged membrane surface (e.g., the PEI- and
MTAC-modified membranes) attracts negatively charged
ionized silica species via electrostatic interactions. The resultant
high concentration of ionized silica species near the membrane
surface led to a faster rate of silica polymerization and facilitated
silica scale formation. The importance of positively charged
functional groups in enhancing silica polymerization has been
demonstrated in biogenic silica formation. Coradin et al.76
reported that electrostatic interactions between positively
charged peptides and negatively charged silica species
promoted silicic acid polymerization. Conversely, more
negatively charged membranes (e.g., the PAA-modified
membrane) repel ionized silica species. Thus, the concentration
of active ionized silica species was relatively lower near the
membrane surface, resulting in reduced silica scaling.
As discussed earlier in the paper, colloidal silica particles
could form by homogeneous nucleation near the membrane
surface; hence, their role in silica scaling cannot be excluded in
the current study. Silica has an isoelectric point at pH ∼ 2,77
rendering the silica particles negatively charged at the near
neutral pH used in our RO scaling experiments (Figure S10).
Thus, colloidal silica particles are attracted by a positively
charged membrane surface and repelled by a negatively charged
surface, which could also support our proposed mechanism for
the impact of membrane surface charge on silica scaling.
Implications. We have demonstrated that membrane
surface charge, rather than membrane hydrophilicity and free
energy of heterogeneous silica nucleation, governed RO silica
scaling. Table S2 in the Supporting Information further
illustrates the interplay between membrane surface properties
and the propensity for RO silica scaling. RO membranes with a
high density of negative surface charge were found to have a
lesser extent of scaling. However, negatively charged carboxyl
functional groups enhance organic fouling by complexation
with calcium ions that form intermolecular bridges among
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Environmental Science & Technology
organic foulant molecules.78−80 Accordingly, membranes with
improved silica scaling resistance may be potentially con-
strained by their high organic fouling propensity when treating
feedwaters with high content of both organic foulants and silica.
On the other hand, despite their potential to increase silica
scaling, positively charged polymers, such as PEI and MTAC,
have been applied to increase membrane resistance to organic
and biological fouling, respectively.31,60,81 As a result, a trade-off
between antiscaling and antifouling membrane properties may
exist when designing high-performance RO membranes. When
RO membranes are exposed to a mixture of silica and other
foulants, their performance is determined by the combined
effect of silica−membrane, silica−foulant, and foulant−
membrane interactions. Although this trilateral process is
complex and beyond the scope of the current study, it should
be considered when designing fouling- and scaling-resistant RO
membranes.
■
ASSOCIATED CONTENT
*
S Supporting Information
The Supporting Information is available free of charge on the
ACS Publications website at DOI: 10.1021/acs.est.6b06411.
Details on the calculation of the wetting function ( f(θ))
to estimate the free energy for heterogeneous nucleation,
DLS measurement of the feedwater used in the silica
scaling test, schematic of heterogeneous silica nucleation
on membrane surfaces (Figure S1), SEM micrographs of
the control and modified membranes (Figure S2), AFM
analysis of the membranes (Figure S3), ATR-FTIR
spectra of the membranes (Figure S4), effects of ethanol
treatment on transport properties of the membranes
(Figure S5), silica scaling results of the control
membrane (Figure S6), SEM micrographs of membranes
after silica scaling (Figure S7), DLS results (Figure S8),
correlation of the extent of silica scaling to membrane
surface charge quantified by zeta potential at pH 7
(Figure S9), zeta potential of silica particles formed in
the RO feed solution at the membrane surface after
considering the effect of concentration polarization
(Figure S10), contact angles and surface energy data of
the membranes (Table S1), membrane surface properties
and silica scaling propensity of modified membranes as
compared to the control membrane (Table S2) (PDF)
■
AUTHOR INFORMATION
Corresponding Author
*Phone: +1 (203) 432-2789. E-mail: menachem.elimelech@
yale.edu.
ORCID
Menachem Elimelech: 0000-0003-4186-1563
Author Contributions
∥ (18) Mukhopadhyay, D. Method and apparatus for high efficiency
T.T. and S.Z. contributed equally.
Notes
The authors declare no competing financial interest.
■ ACKNOWLEDGMENTS
We acknowledge the support received from the National
Science Foundation through the Engineering Research Center
for Nanotechnology-Enabled Water Treatment (ERC-
1449500) and a fellowship awarded by the China Scholarship
Council to S.Z. We also thank Dr. Michael Rooks for his
4404
Article
technical assistance and gratefully acknowledge the use of SEM
and AFM facilities supported by the Yale Institute for
Nanoscience and Quantum Engineering (YINQE). DLS and
zeta potential measurements were performed in the Facility for
Light Scattering (FLS) at Yale University.
■
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4406 DOI: 10.1021/acs.est.6b06411

Environ. Sci. Technol. 2017, 51, 4396−4406

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