Article

pubs.acs.org/est

Molecular Mechanisms of Ultraltration Membrane Fouling in

Polymer-Flooding Wastewater Treatment: Role of Ions in Polymeric
Fouling
Guicai Liu, Shuili Yu,*, Haijun Yang, Jun Hu,*, Yi Zhang, Bo He, Lei Li, and Zhiyuan Liu

School of Environmental Science and Engineering; State Key Laboratory of Pollution Control and Resource Reuse, Tongji
University, Shanghai, China, 200092

Key Laboratory of Interfacial Physics and Technology, Shanghai Institute of Applied Physics, Chinese Academy of Sciences, PO Box
800-204, Shanghai 201800, P.R. China

Shandong Academy of Environmental Science; Jinan, China, 250013

S Supporting Information
*

ABSTRACT: Polymer (i.e., anionic polyacrylamide (APAM))

fouling of polyvinylidene uoride (PVDF) ultraltration (UF)
membranes and its relationships to intermolecular interactions
were investigated using atomic force microscopy (AFM).
Distinct relations were obtained between the AFM force
spectroscopy measurements and calculated fouling resistance
over the concentration polarization layer (CPL) and gel layer
(GL). The measured maximum adhesion forces (Fad,max) were
closely correlated with the CPL resistance (Rp), and the
proposed molecular packing property (largely based on the
shape of AFM force spectroscopy curve) of the APAM chains
was related to the GL resistance (Rg). Calcium ions (Ca2+) and
sodium ions (Na+) caused more severe fouling. In the presence of Ca2+, the large Rp corresponded to high foulantfoulant
Fad,max, resulting in high ux loss. In addition, the Rg with Ca2+ was minor, but the ux recovery rate after chemical cleaning was
the lowest, indicating that Ca2+ created more challenges in GL cleaning. With Na+, the fouling behavior was complicated and
concentration-dependent. The GL structures with Na+, which might correspond to the proposed molecular packing states among
APAM chains, played essential roles in membrane fouling and GL cleaning.

and HA deposited on the membrane surface. Their nding rst

demonstrated that foulantfoulant adhesion plays a key role in
determining the rate and extent of HA fouling of NF membranes.
Subsequently, the same research group obtained a striking
correlation between the maximum foulantfoulant adhesion
forces and the ux decline rate of organic (i.e., alginate and
natural organic materials) fouling of RO membranes,12 which
suggested that intermolecular adhesion forces can serve as an
indicator of the organic fouling potential. Similar results were
reported for FO membranes using a carboxylate-modied AFM
colloid probe as surrogates of alginate of bovine serum albumin
(BSA), Aldrich humic acid (AHA) and EPS.13,14 Alternatively,
membranefoulant adhesion corresponds to the antifouling
property of membranes. Low adhesion forces between the
organic foulant (i.e., BSA, alginate and NOM) and membrane
surface were observed for superhydrophilic FO membranes that
exhibited high antifouling ability.2 Similarly, large membrane-

INTRODUCTION
Organic polymers, as major foulants of ultraltration (UF)
membranes, are widespread in various waters, such as source
water containing algal organic matter (AOM),1,2 municipal and
industrial wastewater containing extracellular/intracellular polymer substances (EPSs),3,4 laundry wastewater containing
cationic polymers,5 coagulation euent containing synthetic
polymeric coagulants,6 and polymer-ooding wastewater containing anionic polyacrylamide (APAM).79 In particular,
APAM, as an important polymer additive for enhanced oil
recovery from existing brown elds, is abundant in polymerooding wastewater (e.g., at a volume of 3 000 000 m3/d in the
Daqing oilelds in China), with typical APAM concentrations of
320600 mg/L.7,10 Therefore, interpreting the fouling behavior
of organic polymers (e.g., APAM) is of paramount practical
signicance for the sustainable application of UF membrane
technology.
Membranefoulant and foulantfoulant intermolecular
forces have been highlighted in investigations of organic fouling
mechanisms. Elimelech et al.11 utilized atomic force microscopy
(AFM) in conjunction with a carboxylate-modied colloid probe
to quantify the adhesion forces between bulk humic acid (HA)
2016 American Chemical Society

Received:
Revised:
Accepted:
Published:
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August 24, 2015

December 20, 2015
January 5, 2016
January 6, 2016
DOI: 10.1021/acs.est.5b04098
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Scheme 1. Schematic Illustration of Preparations for APAM-tip

foulant adhesion forces led to more severe ux declines at the

initial stage of UF in organic foulant treatment.15 Force curve
shapes can provide information on the single molecular
conguration and intermolecular packing properties,1626
which can be applied to explore the fouling layer structure. For
this purpose, foulant molecules should be covalently bound to
the tip and substrate surface using two types of surface
chemistries based on either the strong chemisorption of thiols
on gold surfaces or the covalent attachment of silanes or alcohols
on silicon oxide surfaces.27
Both the curve shape and force value in AFM force
spectroscopy are possibly related to membrane fouling by the
gel layer (GL) and concentration polarization layer (CPL),
which are two essential factors in the resistance-in-series
model.28 However, the distinct relations between the intermolecular interactions and fouling resistance over the CPL and
GL have been seldom explored. In particular, GL resistance is
closely related to the ux loss during ltration, and the GL
stability corresponds to the chemical cleaning complexity; thus,
both properties are typically utilized to evaluate irreversible
fouling. Nevertheless, there are limited reports of the distinction
between intermolecular interaction and irreversible fouling over
GL resistance and GL stability.
In this study, probe tips and silicon substrates were aminofunctionalized through the covalent attachment of silanes on the
silicon oxide surfaces27,2934 and then covalently bound with
APAM carboxyl functionalities, which were activated with 1ethyl-3-(3-(dimethylamino)propyl)carbodiimide (EDC) and Nhydroxysuccinimide (NHS) in aqueous solution.27,3538 AFM
force spectroscopy of APAMAPAM and APAMmembrane
was used to predict the polymer fouling behavior in the UF
process for water treatment. The objectives of this study were as
follows: (i) to conrm the major foulants (i.e., APAM) in a
plantscale UF facility during polymer-ooding wastewater
treatment and investigate the role of ions in APAM fouling of
polyvinylidene uoride (PVDF) UF membranes (using
simulated solutions); (ii) to discuss foulantfoulant/membrane
intermolecular force spectroscopy in terms of force value, curve
shape and interaction distance; (iii) to distinguish the relationships between the membrane fouling and foulantfoulant
intermolecular interaction over the GL and CPL; and (iv) to
investigate relations between the GL stability and foulant
foulant intermolecular interaction through cleaning experiments.

MATERIALS AND METHODS

Materials and Chemicals. N-Ethyl-N-(3-(dimethylamino)-propyl)carbodiimide hydrochloride (EDC) (98%), Nhydroxysuccinimide (NHS) (98%), 3-aminopropyltriethoxysilane (APTES) and 4-morpholine ethanesulfonic acid hydrate
(MES) were obtained from Aladdin. Toluene (99.99%, HPLC
grade) was purchased from Sigma (U.S.). Other reagents used in
all experiments were of analytical grade. Milli-Q puried water
(18.2 Mcm) was used in all experiments.
Anionic polyacrylamide (APAM) was of analytic grade, and its
general structure, molecular weight and degree of hydrolysis can
be found in the Supporting Information (SI), Figure S1. Flat
sheet polyvinylidene uoride (PVDF) UF membranes with a
mean pore size of 50 nm were fabricated at the Shanghai Institute
of Applied Physics (SINAP, China), and their surfaces were
characterized by X-ray photoelectron spectroscopy (XPS) (see
Figure S2). XPS was performed with a RBD upgraded PHI5000C ESCA system (PerkinElmer) with Mg K radiation (h =
1253.6 eV) or Al K radiation (h = 1486.6 eV).
Covalent Modication of Probes and Substrates.
According to previously reported procedures,31,32,3638 the
covalent modication of the probe tips and substrates is
presented in Scheme 1. This novel method included the
activation of APAM and the silanization of wafers (single-crystal
p-type silicon) and tips (spring constant of 0.08 N/m, CSG11,
NT-M DT, Russia). The silanized wafers and probes were
immersed in the APAM (activated by EDC/NHS) solution (20
m/mL in MES buer at pH 8.5) and incubated at room
temperature for 1 h to facilitate amidation. The details of the
covalent modication of the probes and substrates are described
in the SI when presenting Figures S3 and S4.
AFM Force Spectroscopy Measurements. A MultiMode
8 atomic force microscope equipped with a NanoScope V
controller (Bruker, Germany) was employed to perform the
intermolecular force measurements in a liquid cell lled with
freshly prepared inorganic salt solution consisting of pure water;
10, 20, 40, and 80 mM NaCl; and 1.4, 7.0, and 14 mM CaCl2.
Force measurements were obtained between the APAMfunctionalized tips and APAM-modied wafers and between
the APAM-modied tips and PVDF UF membranes.
Foulant Analysis. Element contents of the fouling layer and
polymer-ooding wastewater were obtained on an S-2360N
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Table 1. Element Content and Foulant Content of the Actual Feeding Water and Membrane Foulants
element content (atom percent (at%))

foulant content ((weight percent (wt %))

sample

Na

Ca

APAM

Oil

Na

Ca

actual feeding water

membrane foulants

29.95
48.73

19.29
17.23

30.39
19.59

15.15
6.91

0.13
1.81

29.42
66.34

2.56
1.62

63.96
13.58

3.58
15.92

Figure 1. Membrane ux decline curves: (a) comparison of Na and Ca with identical ionic strength, (b) role of the Ca concentration, (c) role of the Na
concentration, and (d) the comparison between the CPL resistance (Rp) and GL resistance (Rg). For (a), Without: APAM solution without addition of
salts, Na (i.e., 40Na): APAM solution with addition of 40 mM NaCl, Ca (i.e., 14Ca): APAM solution with addition of 14 mM CaCl2; for (b), Without:
APAM solution without addition of salts, 14Ca, 7Ca and 1.4Ca: APAM solution with addition of 14 mM CaCl2, 7 mM CaCl2+20 mM NaCl and 1.4 mM
CaCl2+37.0 mM NaCl; for (c), Without: APAM solution without addition of salts, 10Na, 20Na, 40Na, 80Na: APAM solution with addition of 10 mM,
20 mM, 40 mM, and 80 mM Na; for (d), Without: APAM solution without addition of salts, 10Na, 20Na, 40Na, 80Na, and Ca: APAM solution with
addition of 10 mM Na, 20 mM Na, 40 mM Na, 80 mM Na, and 14 mM Ca. J0 is the permeation ux of the virgin membrane with pure water.

CPL was further rinsed with 200 mL of DI water at a stirring

speed of 300 rpm for 15 min. Subsequently, this membrane was
placed in a beaker containing 300 mL of a sodium hypochlorite
solution (at a mass percent of 0.2% and a pH of 12, adjusted with
sodium hydroxide), where it remained for 1 h at ambient
temperature (2530 C) to clean the GL and then rinsed with
adequate DI water to remove the residual chemical solution. The
permeation uxes of this membrane with DI water were recorded
(under 0.05 MPa) after the physical rinsing of the CPL and the
chemical cleaning of the GL, respectively, which were applied to
estimate the ux recovery rate and calculate the resistance of the
fouling layer. At least three replicates of the fouling and cleaning
experiments were performed for each electrolyte.
Fouling Resistance. The resistance-in-series model, which is
based on Darcys law, was applied to evaluate the characteristics
of membrane fouling.28 For constant pressure ltration, the
resistance-in-series model is expressed as40

system (HITACHI). Correspondingly, the concentrations of

calcium and sodium were determined on an inductively coupled
plasma emission spectrometer (ICP-Agilent 720E), and the
concentrations of APAM and oil were determined based on
previous reports.39 The fouling layer was obtained from a plant
scale UF facility during polymer-ooding wastewater (see SI
Table S1) treatment in Daqing oileld in China.
Fouling and Cleaning Experiments. The UF fouling
experiments were conducted in a dead-end ltration system.39
First, the feeding solutions were obtained by adding 400 mg/L
APAM to the various electrolytes, which were identical to those
used in the AFM force measurements. Then, the feed solution
was ltered through a PVDF membrane under a constant transmembrane pressure (TMP) of 0.05 MPa for 200 min.
At the end of ltration, the fouled membrane was detached and
rinsed with deionized (DI) water to clean the CPL; this
membrane was then installed in the ltration system, and the
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Figure 2. Impacts of Na+ and Ca2+ on the APAMAPAM intermolecular interactions: (a) and (b): comparison of the inuence of Na+ and Ca2+ (with
identical ionic strength) on approaching force curves and rupture force curves, respectively; (c) and (d): impacts of the concentration of Ca2+ on
approaching force curves and rupture force curves, respectively; (e) and (f): impacts of the concentration of Na+ on approaching force curves and
rupture force curves, respectively. The force curves in (e) and (f) were measured in pure water, 10 mM, 20 mM, 40 mM, and 80 mM Na, sequentially,
using the same tip and substrate both of which were covalently grafted by the APAM molecule. Herein, the tested solutions were the inorganic salt
solutions (without any addition of APAM), which had the same concentrations as the feeding solution used in Figure 1.

J=

P
(R m + R f )

R f = R rev + R irev
(1)

(2)

Here, the CPL resistance (Rp) and the GL resistance (Rp) are
denoted by Rrev and Rirrev, respectively. The permeation ux of the
membrane with pure water as the virgin membrane, the fouled
membranes without any cleaning, and the fouled membranes
after physical rinsing are denoted by J0, Jf, and Jg, respectively, and
expressed as in eqs 35:

where J is the permeation ux, P is the trans-membrane pressure,

is the permeate viscosity, Rm is the inherent membrane
resistance, and Rf is the total fouling resistance. Rf is the sum of
hydraulically reversible (Rrev) and irreversible (Rirrev) fouling
resistances:
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J0 =

P
R m

(3)

Jf =

P
(R m + R p + R g)

(4)

Jg =

P
(R m + R g)

(5)

the corresponding intermolecular force curves and surface

morphology.
There were relatively slight changes in the ux loss for Ca2+
with dierent concentrations, as shown in Figure 1(b); however,
the ux loss varied with dierent concentrations of Na+ (see
Figure 1(c)), which can be better expressed by a relative ux (ux
with pure APAM solution acted as the denominator). At the end
of ltration, the relative ux was 1.00 in pure APAM water, and
was increased to 1.13, then was restored to 0.92, nally was
decreased further and reached a minimum of 0.68, followed by an
increase to 0.91, respectively, by the addition of 10 mM, 20 mM,
40 mM, and 80 mM NaCl.
The Rp and Rg of all feeding solutions used in the fouling
experiments are presented in Figure 1(d). Rp was larger than Rg in
all cases, indicating that the concentration polarization had a
greater impact on the ux loss than the GL, which is the reason
for the sharp ux decline at the initial ltration stage. Rp was
enhanced and Rg was decreased by adding Ca2+ compared to
pure water; conversely, Rp and Rg exhibited dierent tendencies
in the presence of Na+. Comparing Rp and Rg with the ux loss
indicates that the aggravation of ux loss in the presence of Ca2+
and Na+ was attributed to the increase in Rp and Rp, respectively,
based on Equation 4. Accordingly, a distinction was made
between intermolecular interaction and membrane fouling over
Rp and Rg to understand the molecular mechanisms of the
polymer fouling of UF membranes, as described later in this
paper.
Intermolecular Force Curves and Molecular Packing
Property. Corresponding to the membrane ux loss and fouling
resistance, the foulantfoulant and foulantmembrane intermolecular force curves and the molecular packing property of the
foulant are presented below.
(i). Roles of Na+ and Ca2+ in FoulantFoulant Intermolecular Interactions. As shown in Figure 2(a), the APAM
APAM approaching intermolecular forces were repulsive (+2.57
nN at 5.4 nm), slightly repulsive (+1.49 nN at 5.4 nm), and
signicantly attractive (4.11 nN at 4.9 nm) for pure water (i.e.,
Without), Na, and Ca, respectively, and the interaction distances
were 147.9, 19.9, and 27.8 nm, respectively, as the tip approached
the surface of the membrane and substrate. Moreover, the
attractive force curve had a typical single sawtooth pattern in the
presence of Ca2+. Considering the interaction distance and curve
shape of these aforementioned approaching forces in pure water,
the major repulsive force was the electrostatic repulsion17,18,24
between the carboxylates of the APAM molecules covalently
grafted on the tip and those on the substrate. By adding 40 mM
NaCl (i.e., Na), sodium ions (Na+) were bound as counterions
around these negatively charged carboxyl groups, and the Debye
screening length of this electrolyte was reduced from 960 nm for
pure water to 1.52 nm (see SI Table S2); thus, both the value and
interaction distance of the electrostatic repulsion were reduced.
In the presence of 14 mM CaCl2 (i.e., Ca), divalent calcium ions
(Ca2+) acted as a bridge to coordinate the carboxylates on the tip
with those on the substrate, and the overall intermolecular Ca2+
binding force became much larger than the electrostatic
repulsions,11,12 resulting in the net attractive approaching force.
Upon retracting the tip from the sample, the curve often
displays a hysteresis referred to as the rupture force (i.e., adhesion
force). As shown in Figure 2(b), the maximum adhesion forces
(Fad,max) for APAMAPAM were 13.23 nN for pure water (i.e.,
Without), 9.10 nN for Na, and 26.68 nN for Ca. In the
presence of Ca2+, Fad,max was largest due to the strong
coordination bonds11,12,45 of the Ca2+-bridging carboxylates

After measuring J0, Jf, and Jg under a TMP of 0.05 MPa, Rm, Rg,
and Rp are given by eqs 68:
Rm =

K
P
=
J0
J0

(6)

Rg =

K (J0 Jg )
P
P

=
J0 Jg
Jg
J0

(7)

K (Jg Jf )
P
P

=
Jf
Jg
Jg Jf

(8)

Rp =

where K is equal to P/.

In the calculation of the fouling resistance, is the permeate
viscosity of pure water, and P is the TMP, which is constant;
thus, the parameter K is a constant. In this paper, Rg/K and Rp/K
are applied to represent Rg and Rp, respectively.

RESULTS AND DISCUSSION

Major Foulants and Polymeric Fouling. The element
contents and foulant contents of the feeding water (i.e., the actual
wastewater) and of the fouling layer for the PVDF UF membrane
are presented in Table 1. The element contents (atom percent
(at%)) of C and Ca increased from 29.95 and 0.13 in the feeding
water to 48.73 and 1.81 in the fouling layer, respectively, during
UF in the polymer-ooding wastewater treatment. Correspondingly, the contents (weight percent (wt %)) of APAM and Ca in
the eluate from the fouled membranes increased from 29.42 and
3.58 to 66.34 and 15.92, respectively, whereas that of oil and Na
decreased from 2.56 and 63.96 to 1.62 and 13.58, respectively.
Accordingly, APAM7,41,42 and the coexisting divalent metal ions
had dominant roles in membrane fouling. The role of Na+ in
APAM fouling cannot be ignored because it can bind around the
interface of the carboxylates of APAM in the fouling layer,43,44 in
addition the high concentration of Na+ (at a wt % of 63.96) in the
feeding water. Herein, the impacts of metal ions (e.g., Ca and Na)
on APAM fouling of UF membranes (with simulated feeding
solutions) are presented in Figure 1, including membrane ux
loss and fouling resistance.
The comparison of ux loss with and without Na and Ca is
presented in Figure 1(a). The total ionic strength of inorganic
salt added in the APAM feeding solution was 40 mM for NaCl
(i.e., Na) and CaCl2 (i.e., Ca), and no metal ions were added in
the Without experiment as a control. Similar to previous
studies,1,11 Ca2+ enhanced the ux loss by forming complexes
with APAM and neutralizing the negative charges of APAM
molecules more eectively than monovalent cations. Unexpectedly, Na+, as a monovalent cation, resulted in nearly the same ux
loss as with Ca2+, even though the total ionic strength of Na was
identical to that of Ca. This serious ux loss with Na is attributed
to the fouling layer structure of the interpenetrating polymer (i.e.,
APAM) network, which is discussed in detail when presenting
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Figure 3. Schematic representation of the roles of Na+ concentration in the APAMAPAM intermolecular interactions for (a) Without, (b) 10 Na, (c)
20 Na, (d) 40 Na, and (e) 80 Na. Upper part: the schema of the foulantfoulant interaction at the moment of the maximum adhesion force acting upon
the tip; middle part: the schema of the foulantfoulant attraction; lower part: the schema of the foulantfoulant repulsion. Red, blue, gray and white
spheres are oxygen, nitrogen, carbon and hydrogen atoms, respectively. Additionally, (a): IHBs I: NHOOC, IHBs II: CHOOC, and
(d): Coil-up I: cohesion entanglement, Coil-up II: topological entanglement. The number of + represents the strength of the electrostatic repulsion
among the APAM carboxyl groups.

mentioned above. Compared to pure water, the presence of Na+

in water weakened the adhesion and repulsion forces between
APAM molecules, instead of strengthening the adhesion force as
expected, indicating the destruction of certain bonds that can be
generated in pure water. Hydrophobic attraction is typically the
favorable interaction among the nonpolar hydrocarbon segments
of the APAM chains.2 Alternatively, the hydrogen bonds of N
HOCO43,44 and CHOCO46 and the specic ionic
hydrogen bonds (IHBs)47 of NHOOC, HO
HOOC, and CHOOC typically contribute to the
APAMAPAM rupture force. The Fad,max and force curve shape
suggests that the hydrophobic attraction plus hydrogen bonding
was stronger than the electrostatic repulsion, rendering a net
attractive rupture force in pure water. However, the formation of
the hydrogen bonds was more likely impeded by the addition of
sodium ions,48 thus resulting in the decrease of Fad,max with Na
compared to pure water.
There are three major sequential plateaus in the APAMNaAPAM rupture force curve: Plateau 1, Plateau 2, and Plateau
3 with average values of 8.4 nN, 4.4 nN, and 1.9 nN,
respectively, as shown in Figure 2(b). The plateau-like pattern
indicates that the APAMAPAM interactions were under a
nonequilibrium condition,18,20 which should represent the
overlap among the tip-APAM and substrate-APAM chains, and
the number of plateaus approximately corresponded to the
number of APAM chains that were entangled together.17,20 For
the same reason, the interaction distance of APAMNaAPAM
was 820 nm longer than that of APAMwaterAPAM or
APAMCaAPAM.23 This wide interaction distance, in
conjunction with the multiple plateaus, likely indicates that
more than three APAM chains signicantly coiled up
intermolecularly with the addition of Na.1721,2326,49 In

contrast, the typical single sawtooth pattern for Ca and pure

water indicates that APAMAPAM interactions were under
equilibrium conditions, which may correspond to less
intermolecular overlap.1720 Na+ might have played an
important role in the molecular conguration and the molecular
packing property of APAM chains, which was elaborately
discussed for Figure 3.
The impacts of the concentration of Ca2+ on APAMAPAM
interactions are presented in Figure 2(c) and (d). The maximum
force value, interaction distance and curve shape were nearly the
same for all tested concentrations of Ca2+ for the rupture and
approaching force curves, indicating that the molecular packing
property and intermolecular adhesion were independent of the
Ca2+ concentration. This is consistent with the similar ux loss
measured for a series of Ca2+ concentrations (see Figure 1(b)).
However, the APAMAPAM intermolecular force curves varied
with the concentrations of Na+ (see Figure 2(e) and (f)), which is
consistent with the changes in ux loss (see Figure 1(c)).
As presented in Figure 2(f), the Fad,max for pure water (i.e.,
Without) was larger than that for all of the tested NaCl
electrolytes likely due to Na+ impeding the formation of the
intermolecular hydrogen bonds, as mentioned above. For the
same reason, the destruction of the IHBs led to more free

OOC groups on the APAM molecules, and the 10 mM and 20

mM Na+ provided slight double layer compression on these free
APAM carboxylates,12 enhancing the approaching repulsion
compared to that with pure water (see Figure 2(e)). However, as
the concentration of NaCl increased to 40 mM or 80 mM, the
double layer compression became prominent,11,12 thereby
decreasing the APAMAPAM approaching repulsion even
though there were more OOC groups than in pure water.
Moreover, the signicant reduction of electrostatic repulsions for
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Figure 4. Relationships between membrane fouling and intermolecular interaction. (a) correlation between Rp and the maximum
APAMsolutionAPAM adhesion forces, (b) relation between Rg and the proposed molecular packing property. For (b), R & P represented
regular and porous, and the number of + and represented the increase and decrease of regularity and porosity, respectively; D-rods: dispersed
rods, A-rods: agminated rods, E-coils: expanded random-coils, S-coils: sphere-shaped coils.

40 Na or 80 Na led to the larger Fad,max compared to 10 Na or 20

Na.
In contrast to the insignicant changes in the repulsion values
between 10 Na and 20 Na and between 40 Na and 80 Na, there
were prominent changes in Fad,max attributed to the dierence in
molecular packing states, rather than electrostatic repulsions.11
For the same reason, the rupture force curves experienced
signicant changes in curve shape with all of the tested NaCl
solutions in contrast to the approaching force curves (see Figure
2(e) and (f)). Based on the relations between the shapes and
interaction distances of the rupture force curves discussed above,
the intermolecular overlap was more extensive with 20 Na than
with 10 Na, rendering a larger Fad,max for the higher sodium
concentration. Unexpectedly, the overlap with 80 Na was abated,
but Fad,max was enhanced compared to that with 40 Na, which had
the most extensive overlap among APAM chains. This is likely
due to the change in molecular conguration of single APAM
chains (see Figure 3).
(ii). Roles of Na+ and Ca2+ in FoulantMembrane
Intermolecular Interactions. The APAMmembrane intermolecular interactions in all of the tested electrolytes are presented
in SI Figure S5. The inuencing mechanism of Na+ and Ca2+ on
the APAMmembrane interaction was identical to that for
APAMAPAM, on account of the similar carboxylate groups on
the membrane surface (see SI Figure S2) as APAM. Nevertheless, there were dierences between the APAMAPAM and
APAMmembrane interactions under dierent experimental
conditions. In pure water, the repulsive rupture force for
APAMmembrane, which diered from the attractive rupture
force for APAMAPAM, indicates that the intermolecular
hydrogen bonds plus hydrophobic attractions were not sucient
to neutralize the electrostatic repulsion between APAM and the
membrane. There were almost no changes in the interaction
distance, curve shape, and Fad,max of the APAMmembrane
rupture force curve for all concentrations of Na+, which indicates
that the molecular packing state of polymeric organics (e.g.,
APAM) on the surface diered from that among the polymer
chains.
(iii). Roles of Na+ and Ca2+ in the Molecular Packing
Properties. The molecular packing properties of APAM in all
tested electrolytes are proposed in this section based on all of the
above-mentioned discussion of the AFM force curves and on the

scanned AFM imagines of the fouled membrane surfaces (see SI

Figure S6). In the presence of Ca2+, the APAM molecular
packing state can be explained by the egg-box model50 in which
calcium ions preferentially bind to the oxygen atoms of
carboxylates in a highly organized manner and form bridges
between adjacent APAM molecules, leading to the egg-boxshaped gel network.1 The schematic illustration of the proposed
molecular packing property of APAM in the presence of Na+ is
presented in Figure 3.
In Figure 3, the polymerization25 of hydrogen-bonds (between
CO/OOC and NH/CH) in pure water (i.e.,
Without) led to a macromolecular structure (i.e., hydrogen
bonded network46). The addition of Na+ impeded the formation
of intermolecular hydrogen bonds, and the APAM molecular
packing state then depended mainly on electrostatic repulsion11,20 and the salting-out eect of Na+ and Cl.25,5153 In the
presence of 10 mM Na+, the prominent electrostatic repulsion
caused the single chains to expand11,53 and simultaneously led to
the enhancement of molecular stiness, as well as the reduction
of the intermolecular overlap in the GL; thus, the APAM
molecules could be viewed as dispersed rigid rods. The
addition of 20 mM Na+ enhanced the molecular exibility of the
APAM rigid rods due to an enhanced salting-out eect,25,52
which facilitated the intermolecular overlap, although the
detected electrostatic repulsion was still notable; thus, the
APAM molecular chains in the GL could be viewed as agminated
rigid rods. When the concentration of Na+ was increased to 40
mM, the electrostatic repulsion was signicantly abated; thus, the
molecular exibility was further enhanced, and the rigid rods
were spontaneously converted into expanded randomcoils22,25 according to the principle of increasing entropy.
Simultaneously, the random APAM coils entangled together
intermolecularly to create the interpenetrating polymer network.
Finally, in the 80 mM NaCl solution, the expanded random coil
collapsed into a sphere-shaped structure likely due to an
enhanced attraction among the Gaussian segment24 of an
APAM chain, around which the amount of free solvent (i.e.,
water) molecules was reduced because more water molecules
were orientationally bound to Na+ and Cl to form hydrated ions
(i.e., salting-out eect).25,51,52
In summary, APAMAPAM adhesion was a net force of
electrostatic repulsions among carboxylate groups, hydrogen
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Figure 5. The ux recovery rate for the GL was signicantly

higher than that for the CPL with all tested feeding solutions,

bonds and hydrophobic attractions in pure water (i.e., Without).

By adding NaCl, the IHBs were destroyed, and the electrostatic
repulsions were reduced by double layer compression. Moreover,
the Fad,max (between APAM molecules), molecular packing
property, and ux loss were dependent on the concentrations of
Na+. The strong bonds formed by Ca2+ coordinating the
carboxylate groups were crucial to the ux loss in the presence of
Ca2+. The relations between intermolecular interactions and
fouling need further investigation.
Relationship between Fouling and FoulantFoulant
Intermolecular Interactions. The foulantfoulant, rather
than foulantmembrane, intermolecular interactions were
closely related to membrane fouling. Rp was strongly correlated
with the foulantfoulant Fad,max (see Figure 4(a)), and Rg was
closely related to the GL structure that corresponded to the
molecular packing property of the foulant (see Figure 4(b) and
SI Figure S6).
There was a striking correlation between the foulantfoulant
Fad,max and Rp, as displayed in Figure 4(a). The enhancement of
the APAMAPAM Fad,max could have rendered the increase in
Rp, resulting in more severe ux loss by the CPL. The Ca2+
bridging force, electrostatic double layer compression eect, and
salting-out eect were responsible for the changes in Rp. In fact,
Rp is of the nature of osmotic pressure caused by the
concentration gradient between the CPL (at a high concentration probably exceeding the dilute/semidilute threshold C*54)
and the permeation (at a low concentration), which was
determined by the diusion coecient (D) of foulant under
constant extrinsic conditions. The large foulantfoulant
adhesion force may have corresponded to a small D and thereby
caused the high concentration gradients between the CPL and
bulk solution and between the CPL and permeation (according
to Ficks rst law), as well as the high Rp (based on the Vant Ho
equation).
The proposed molecular packing properties, in conjunction
with the measured AFM images of the fouling layers (see SI
Figure S6), were related to the GL resistance, as shown in Figure
4(b). Rg increased according in the following order: Ca <
Without < 80 Na < 10 Na < 40 Na < 20 Na. The packing layer of
agminated rods that formed with 20 Na provided the highest
resistance (Rg/K) of 1.40205. The egg-box-shaped gel network of
Ca exhibited the lowest resistance of 0.50303, although the total
ux loss for Ca was higher. The regular and well-organized pore
structure, such as the egg-box-shaped gel network formed by
Ca2+ bridging carboxylates in a highly organized manner,50 and
the macromolecular structure created by hydrogen bond
polymerization in pure water46 could render a low Rg. In
contrast, the slightly porous structure that was formed by
intermolecular overlap in a random manner, such as the
interpenetrating polymer network of 40Na and the agminatedrod packing layer of 20 Na, corresponded to a high Rg.
Overall, the strong correlation between Fad,max and Rp indicates
that Fad,max can serve as an indicator of CPL fouling potential.
Alternatively, the molecular packing property was responsible for
the GL structure, which can be used to predict Rg. The sum of Rp
and Rg determines the membrane ux based on eq 4. An overview
of the molecular mechanisms of APAM fouling for the PVDF UF
membranes is presented in SI Figure S7.
Flux Recovery Rate and Chemical Stability. The ux
recovery rate after cleaning was investigated to further
understand the specic roles of sodium and calcium ions in
APAM fouling. The ux recovery rates after physical ushing of
the CPL and after chemical cleaning of the GL are presented in

Figure 5. Flux recovery rate of APAM-fouled membranes for Without,

10 Na, 20 Na, 40 Na, 80 Na, and Ca, after physically rinsing with water
and chemical cleaning with agents (same cleaning method used in all
cases). Herein, Baseline is the normalized ux at the end of ltration.

although Rg > Rp. The GL (stably adsorbed onto the membrane

surface) was crucial to membrane ux recovery according to
Darcys law.
As shown in Figure 5, the ux recovery rates after chemical
cleaning in the same method increased as Ca < 40 Na < 10 Na
20 Na < Without 80 Na, which was dierent from the order of
Fad,max for APAMAPAM or interactions. With Ca, although Rg
was minor, the ux recovery rate was the lowest in all of the tested
electrolytes due to the chemically stable coordination bonds that
corresponded to the largest APAMAPAM Fad,max. This
indicates that nature of the intermolecular force played an
essential role in GL stability that had no direct relation to Rg. In
contrast, although the Fad,max of 40Na was not the largest in all of
the tested NaCl solutions, the ux recovery rate was the lowest
likely due to the stable structure of the interpenetrating polymer
network that was created through the expanded random-coils
coiling up. Moreover, in spite of the higher Fad,max with 80 Na, the
ux recovery rate was the highest, possibly due to the sphereshaped structure of GL. The GL structure could have also played
an important role in the GL stability, under the Fad,max of identical
nature (e.g., hydrogen bonds, hydrophobic attractions, and
coordination bonds).
In this study, a distinction between intermolecular interactions
and fouling behavior over the CPL and GL was made to
understand the molecular mechanisms occurring in the fouling of
UF membranes by APAM in polymer-ooding wastewater.
Because Fad,max was strongly correlated to Rp, APAMAPAM
adhesion must be taken into account in controlling concentration polarization. Alternatively, the molecular packing
property of APAM, which was responsible for Rg, could be
used to predict the irreversible fouling potential. In addition, the
GL stability depended on the nature of the intermolecular forces,
which can provide a fundamental basis for the choice of reagent
for cleaning APAM GL. These results are promising for the
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polymers.

ASSOCIATED CONTENT

S Supporting Information
*

The Supporting Information is available free of charge on the

ACS Publications website at DOI: 10.1021/acs.est.5b04098.

Additional information as noted in the text, Figures S1

S7, Table S1S2 (PDF)

AUTHOR INFORMATION

Corresponding Authors

*(S.Y.) Phone: 02165982708; e-mail: ysl@tongji.edu.cn.

*(J.H.) Phone: 02139196392; e-mail: hujun@sinap.ac.cn.
Notes

The authors declare no competing nancial interest.

ACKNOWLEDGMENTS
This research was nancially supported by the National Natural
Science Foundation of China (No. 51578390), Shanghai Pujiang
Program (No. 14PJ1432400), and the National Water Pollution
Control and Treatment Key Technologies R&D Program (No.
2012ZX07403-001).

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