Chemical Engineering Journal 309 (2017) 30–40

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Chemical Engineering Journal

journal homepage: www.elsevier.com/locate/cej

Surface modified glass fiber membranes with superior chemical and

thermal resistance for O/W separation
Zhanping Cao, Tingyu Hao, Pan Wang, Yufeng Zhang, Bowen Cheng, Tao Yuan, Jianqiang Meng ⇑
State Key Laboratory of Separation Membranes and Membrane Processes, Tianjin Polytechnic University, Tianjin 300387, China

h i g h l i g h t s

HPEI was grafted on glass fiber membranes via a two-step process.

Surface grafting improves membrane hydrophilicity, flux and oil rejection.

The membranes show high permeation and quantitative oil rejection.

The membranes are robust to various chemicals except strong alkalis.

The membranes are robust to long-term boiling treatment.

a r t i c l e i n f o a b s t r a c t

Article history: The exploration of novel O/W filters having not only high permeation and rejection but also durable per-
Received 4 August 2016 formance is a key driver of membrane material research. In this study, a glass fiber membrane (GF) was
Received in revised form 3 October 2016 grafted with hyperbranched polyethyleneimine (HPEI) via a two-step process and used for O/W separa-
Accepted 4 October 2016
tion. The silanol group in the GF was reacted with epichlorohydrin followed by the reaction with the
Available online 5 October 2016
amine groups in the HPEI molecules. The obtained GF-g-HPEI membranes were characterized by FTIR,
XPS, SEM and WCA measurements. The O/W separation performance was evaluated by dead-end filtra-
Keywords:
tion of a series of oil dispersion and emulsions. ATR-FTIR and XPS measurements indicated that HPEI was
Glass fiber membrane
O/W separation
grafted on GF membrane surface successfully. The engineered GF membranes exhibit superwetting prop-
Surface grafting erties, outstanding permeability (1000 L/m2h at 10 cm gravity pressure) and quantitative oil rejection
Hyperbranched polymer (=99.6%) for emulsified and dispersed oil. In addition, the modified membrane showed excellent thermal
Superhydrophilicity and chemical stability, compared with polymer-based membranes. All the above characteristics render
the modified GF membrane cheap, effective and durable filters for O/W emulsion separation.
Ó 2016 Elsevier B.V. All rights reserved.

1. Introduction
With the continuous development of petrochemical, metallur-
gical, pharmaceutical and the food industries etc, a large amount
of oily wastewater is produced every day [1]. There are many toxic
substances in oily wastewater that severely harm aquatic
resources human health and affect crop growth. Hence, the devel-
opment of effective and cheap oil/water (O/W) separation methods
is imminent. Conventional oily wastewater treatment methods,
namely gravity separation, air flotation, coagulation, electrochem-
ical and biochemical methods, have the intrinsic disadvantages
such as low efficiency, high operation cost, equipment corrosion
and recontamination problems [2,3]. Recently, membrane
⇑ Corresponding author.
E-mail addresses: jianqiang.meng@hotmail.com, jianqiang_meng@126.com
(J. Meng).
filtration has been widely used in research for O/W emulsion treat-
ment with distinct advantages of low cost, small footprint, and
steady permeate quality [4,5].
In recent years, various membranes, such as filter paper, metal
meshes, polymer membranes, ceramic membrane, textiles and
carbon nanotube hybrid membranes, have been studied for O/W
separation [6–9]. Among the filtration materials, polymeric mem-
branes [10,11] have attracted the most attention due to easiness
of fabrication, low cost and good mechanical integrity. However,
the O/W emulsions in the field can have corrosive components
and high temperatures and the membranes usually is exposed to
routine rinse in harsh conditions, the application of polymeric
membranes is limited due to their low thermal and chemical resis-
tance. Obviously, in this context, glass fiber membranes can be a
good alternate due to their easily modifiable surface, superior ther-
mal and chemical resistance, fair mechanical strength, recyclability
and low cost. In fact, there has already been a report using

http://dx.doi.org/10.1016/j.cej.2016.10.013
1385-8947/Ó 2016 Elsevier B.V. All rights reserved.
 Z. Cao et al. / Chemical Engineering Journal 309 (2017) 30–40
zwitterion-grafted membranes for O/W separation [12]. Surface
superhydrophilicity was claimed for the membrane and superior
O/W separation performance was demonstrated [13,14]. However,
the membrane was prepared by surface initiated ATRP of
methacrylate monomers [15]. Strict condition and inert atmo-
sphere were required and limit the fabrication in scale. Hyper-
branched polyethyleneimine (HPEI) is a spherical molecule with
abundant hydrophilic amine groups at the periphery. In aqueous
solution, a large amount of water molecules can bond with the
HPEI molecule firmly via hydrogen bonding. In this work, we
report the fabrication of cheap and superhydrophilic HPEI-grafted
glass fiber membranes for separation of oil and water from O/W
mixtures. Fourier transform infrared spectroscopy (FTIR), X-ray
photoelectron spectroscopy (XPS) and Field emission scanning
electron microscopy (FESEM) were used to characterize the change
of chemical composition and surface morphology. The change of
membrane water flux, separation capacity and membrane antifoul-
ing performance upon HPEI grafting were studied by dead-end fil-
tration of both oil dispersion and O/W emulsions. The solvent
resistance of the modified membrane was characterized by solvent
immersion test. The membrane thermal resistance was evaluated
by boiling with water.
2. Experimental section
2.1. Materials and Reagents
Glass fiber (GF) membrane with diameter of 47 mm and aver-
age pore diameter of 0.7 lm was supplied by Millipore, USA. The
polyvinylidene fluoride (PVDF) membrane (Immobilon-P, the aver-
age pore is 0.45 lm) was purchased from Millipore, USA. The
‘‘PVDFAH” membrane was prepared by the method of Yuan using
PVDF membrane as a starting material [6]. The polyacrylonitrile
(PAN) membrane (PA-200, SePRO Co., USA) has a rejection of 85%
to polyethylene glycohol (PEG) (Mw = 20,000). Epichlorohydrin
(EPI) and hyperbranched polyethyleneimine (HPEI) molecules
(Mn = 60,000, 50%; Mn = 10,000, 99%; Mn = 600, 99%) were pur-
chased from J&K Scientifics Ltd. (Beijing, China). Ethanol, 98%
H2SO4, 30% H2O2 and sodium dodecyl sulfate (SDS, AR) were pur-
chased from Tianjin Kermel Chemical Reagent Co, Ltd. Ultrapure
deionized water (DI water, 18.2 MX cm at 25 °C, 1.2 lg/L TOC)
was obtained from a Millipore Milli-Q Advantage A10 water purifi-
cation system (Billerica, MA, USA). All chemicals were used as
received unless otherwise noted.
2.2. Fabrication of the GF-g-HPEI membrane
The reaction mechanism fabricating the GF-g-HPEI membrane
was shown in Fig. 1. The HPEI molecule was bonded onto the mem-
brane surface with epichlorohydrin (EPI) as an intermediate via a
two-step reaction process. Prior to the grafting reaction, the glass
fiber membranes were washed by piranha solution (98% H2SO4:
30% H2O2 (v/v) = 7:3) at 95 °C for 1 h. In this way, the density of
Fig. 1. Reaction mechanism of HPEI grafting onto glass fiber membrane surface.
31
silanol groups [16,17] on the membrane surface increases and their
reactivity can be enhanced for further modification. Then the
membrane was washed to neutral with water and dried at 40 °C.
Afterward, the membrane (diameter of 47 mm) was immersed in
15 mL of solution which was prepared by mixing 10 mL of
1.5 mol/L NaOH and 5 mL of EPI and kept stirring for 12 h at
25 °C [17]. Then the membrane was washed twice with DI water
and dried at 40 °C. Subsequently, the membrane was treated with
ethanol solution of HPEI (25 g/L) at 80 °C for 24 h [18]. Finally, the
membrane was thoroughly washed with 95% ethanol, followed
with drying by vacuum pump at 40 °C until a constant weight
was obtained.
2.3. Characterization
FT-IR spectra of the membrane samples were recorded with a
Vector-22 spectrometer (Bruker Daltonic Inc., Germany) at an inci-
dent angle of 45o with Zinc Selenide (ZnSe) as an internal reflection
element. Each spectrum was signal averaged from 32 scans at
4 cm1 resolution. The surface composition of the membranes
was also analyzed by X-ray photoelectron spectroscopy (XPS, FEI
Co., Ltd., USA) using an Al Ka as the radiation source
(ht = 1486.6 eV) at a pass energy of 93.9 eV. A survey scan was col-
lected over the range of 0–1000 eV, and a high-resolution core-
level spectrum was collected for C1s. The membrane surface mor-
phology was observed by a field-emission scanning electron micro-
scopy (FESEM, Hitachi S-4800 system, Japan). The samples were
dried thoroughly and coated with gold before SEM scanning. The
hydrophilicity of the samples cannot be estimated by the water
contact angle instrument because the membrane surface is very
porous. Membrane surface wettability was evaluated qualitatively
by a method proposed by Xu et al. [19]. They mentioned that when
the water droplet comes into contact with the membrane surface,
it will break into two parts: permeating through the membrane
and spreading on the membrane surface. The higher fraction per-
meating through the membrane compared to the fraction spread-
ing on the membrane surface, the membrane is believed to have
higher hydrophilicity. In this study, 10 lL of water was stained
by rhodamine B and injected on the membrane surface with a
micro syringe. Then the area of the dye solution spreading on the
membrane surface was observed to determine the membrane
wettability.
2.4. Oily emulsion samples preparation
Two surfactant-free oil dispersions, hexadecane in water (Vhex-
adecane: Vwater = 1:2) and N-dodecane in water (VN-dodecane:
Vwater = 1:1) were prepared through ultrasonication for 30 min.
Three surfactant-stabilized emulsions, including SDS-stabilized
hexadecane in water, SDS-stabilized N-dodecane in water and
SDS-stabilized soybean oil in water, were prepared in this study.
The surfactant-stabilized emulsions were prepared by dissolving
1 mL of oil and 10 mg of SDS in 99 mL of water. Then the mixture
32 Z. Cao et al. / Chemical Engineering Journal 309 (2017) 30–40

was stirred at 2000 rpm for 5 h and ultrasonicated for 30 min to 3. Results and discussion
obtain a milky emulsion [20].
3.1. Synthesis of the superhydrophilic glass fiber membrane
2.5. O/W emulsion filtration experiments
There is a large amount of silanol groups on the GF membrane
surface. The silanol group is very polar and has a pKa of 4, and
The water permeation property and O/W separation capability
hence can promote severe non-specific interaction with the surfac-
of the unmodified and modified membranes were carried out using
tants in emulsions. Therefore, the silanol group needs to be end-
a laboratory-made dead-end filtration apparatus. The membrane
capped. Fortunately, the silanol group is easy to be modified. The
was wetted with DI water before testing. Then water or the pre-
alkoxysilane condensation reaction is a straightforward method
pared O/W mixtures were poured onto the top of membrane. The
for glass material modification. We first used three zwitterionic
whole process is driven solely by gravity without any external
silane coupling agents previously used in a cellulose membrane
force and the height of the feed solution was kept constant at
modification process for the silanol group end-capping [25]. We
10 cm at room temperature [21]. The O/W mixture flux was
found that the benefit of this modification method on membrane
recorded as the average flux in the first 5 min filtration. The filtrate
permeation and oil rejection properties is minimal. The low
was withdrawn for ET1020A total organic carbon analysis (TOC,
hydrophilization capacity of the small molecular silane coupling
Euro Tech Ltd., UK) to measure the oil content. Both the feed and
agents should be responsible for this result. HPEI molecules have
the permeate were diluted 22 times to render the TOC of the mea-
abundant amine groups which can easily react with electrophiles
sured samples lower than 300 mg/L. To visualize the oil–water sep-
and bond with water molecules. Therefore, we finally chose HPEI
aration performance, the BX51-P polarizing microscope (Olympus
to modify the GF membrane surface.
Optical Co., Ltd., Japan) was used to observe the difference of the
The grafting yield is an important parameter to characterize the
feed and the collected filtrates. The oil droplet distributions of
modified membranes. The gravimetry method [26] and the TGA
the O/W mixtures were analyzed by a LA-300 laser-scattering par-
[27] are the most two common methods for grafting yield mea-
ticle size distribution analyzer (Horiba Stec, Co., Ltd., Japan). The
surement. However, we found that the membrane mass change
water flux and emulsion flux of the membrane were calculated
by Eq. (1) [11].

Vi GF
Ji ¼ ð1Þ
At a GF-g-EPI
GF-g-PEI60000
where Ji is the water or O/W emulsion flux of membrane (L/m2h), Vi GF-g-PEI10000
is the permeate volume (L), A is the effective area of membrane GF-g-PEI600
(m2), t is the testing time (h). The rejection of membrane to O/W
mixture was calculated with Eq. (2) [22].
 
Ci 780
R¼ 1  100% ð2Þ 3305
C0
680
where Ci and C0 are the oil concentration of the permeate and the
feed emulsion respectively. They were determined by TOC mea-
surements. Three measurements were conducted to obtain the
average flux and rejection values.

2.6. The chemical stability test 500 1000 1500 2000 2500 3000 3500 4000
-1
Wavenumber(cm )
The chemical stability of the membranes was evaluated through
the solvent immersion method [23]. The modified membrane was GF
dried to constant mass at 40 °C. Immediately following the drying GF-g-EPI
step, the dry mass m0, was measured. Then the dry modified mem-
b GF-g-PEI60000
brane was placed in a beaker filled with the solvent or solution and GF-g-PEI10000
GF-g-PEI600
kept shaking for 72 h at 25 °C. After that, the samples were washed
with DI water for 5 h to remove the remaining solution. During this
period, the water was replaced for 2–3 times to clean the residue 1540 1558 1576
solvent thoroughly. Finally, the samples were dried completely,
the weight of the film at this time is denoted as mi. The mass loss
rate (ML) of the membrane was calculated as follows:

m0  mi
ML ¼  100% ð3Þ
m0

2.7. The thermal resistance test

1520 1540 1560 1580 1600
-1
The thermal stability of the membranes was evaluated by Wavenumber(cm )
refluxing with water at 100 °C for 15 days [24]. Then the O/W mix- Fig. 2. ATR-FTIR spectra of GF, GF-g-EPI, GF-g-HPEI60000, GF-g-HPEI10000 and GF-
ture flux, separation performance and surface morphology of the g-HPEI600 membranes (a: full spectra from 500 to 4000 cm1; high resolution
membrane after treatment were re-measured. spectra from 1510 to 1610 cm1).
 Z. Cao et al. / Chemical Engineering Journal 309 (2017) 30–40
upon epichlorohydrin grafting is minimal. The membrane can even
slightly lose mass upon HPEI grafting, which may be related to the
alkaline nature of the HPEI solution leading to slight erosion of the
glass fiber. On the other hand, the method of TGA to measure the
grafting yield of the membranes is not suitable for the GF mem-
brane since the additives and binders in the GF membrane can
interfere. Therefore, the grafting yield of the modified membrane
can only be evaluated qualitatively by the surface spectroscopy
methods such as FTIR and XPS.
3.2. Chemical composition of the membrane surface
The chemical composition of the unmodified and modified
membranes was characterized by FTIR. The typical spectra of GF,
GF-g-HPEI60000, GF-g-HPEI10000 and GF-g-HPEI600 membranes
are shown in Fig. 2. Compared with the GF membrane (Fig. 2a),
the absorption peaks at 680 cm1 and 780 cm1 become promi-
nent for the GF-g-HPEI membrane, which are attributed to the
bending vibration of N–H and C–N bonds that generated in the
ring-opening reaction. In addition, the absorption at 3305 cm1 is
also significantly intensified, which is attributed to the stretching
vibration of N–H and O–H groups that generated in the ring-
opening reactions. For the enlarged infrared spectra from
1510 cm1 to 1650 cm1 (Fig. 2b), three new peaks appear at
1540 cm1, 1558 cm1 and 1576 cm1, which are attributed to
the C–N stretching vibration, bending vibration of the primary
and tertiary amines. Moreover, there is a wide IR absorption at
1000 cm1 attributed to the stretching vibration absorption and
asymmetric stretching vibration absorption of Si–OH, Si–C, Si–O–
Si on membrane surface. The adsorptions at 1400 cm1 are attrib-
uted to in-plane bending vibration of CH2 group in HPEI, which sig-
nificantly increase after HPEI grafting. These observations indicate
GF O1s
GF-g-EPI
GF-g-PEI60000
GF-g-PEI10000 C1s
GF-g-PEI600
Si2p N1s
0 200 400 600
Binding Energy
Fig. 3. XPS wide-scan spectra of GF, GF-g-EPI, GF-g-HPEI60000, GF-g-HPEI10000
and GF-g-HPEI600 membrane surfaces.
Table 1
Surface element analysis of GF, GF-g-EPI, GF-g-HPEI60000, GF-g-HPEI10000 and GF-g-HPEI600 membranes.
Membranes Element (atom %)
C O
GF 23.56
GF-g-EPI 24.81
GF-g-HPEI60000 53.47
GF-g-HPEI10000 57.67
GF-g-HPEI600 50.24
33
that the HPEI molecules were successfully immobilized onto the
glass fiber membrane surface respectively.
The elemental composition of membrane surface was further
analyzed by XPS. From the wide spectra of membranes in Fig. 3,
we can see that the modified membranes have much higher N1s
intensity at 400.00 eV than the unmodified membrane, which is
attributed to high N content in the grafted HPEI molecules. The
corresponding composition of these membrane surfaces is listed
in Table 1. Similarly, the nitrogen content increases and the O/N
element ratio declines sharply. At the same time, we can see the
carbon content booms after HPEI grafting. We believe that the
change is also due to the HPEI grafted on membrane surface and
the change corresponds well with the nitrogen content in HPEI
molecules of different molecular weights.
3.3. Surface morphology and hydrophilicity
The surface morphologies of unmodified and modified mem-
branes (at magnifications of 2K and 30K) are shown in Fig. 4.
From Fig. 4(a0 –d0 ), we can find that the roughness of glass fiber
increases after HPEI grafting. There are some granular nodules
appearing on the fiber surface, which is more obvious for the mem-
brane grafted with HPEI of higher molecular weight and may be
due to HPEI gel dewetting from the glass fiber surface. From the
pictures in Fig. 4(a–d) at a lower magnification, we see the three-
dimensional fabric structure remains intact, indicating that the
membrane is robust to the grafting process. No pore filling phe-
nomena were observed, which is due to the very large pore size
compared to the size of the grafted HPEI molecules.
It is well accepted that superhydrophilic membranes have high
oil and water separation efficiency [21], so the water wettability of
the membranes is a key measurable to evaluate the membrane
performance. At first, we use a Kruss Instrument (CM3250-
DS3210, Germany) to measure the water contact angle (WCA) of
the membrane surface [11,25], but we found that the water dro-
plets can infiltrate the membranes spontaneously so that the
WCA value could not be obtained. In this study, the hydrophilicity
of the membranes was evaluated by observing the pattern and area
of the dye solution spreading on the membrane surface. The pic-
tures are shown in Fig. 5. We can see that the stained area on
the modified membrane surface appears to be circular, while that
on the unmodified membrane surface shows an irregular shape.
Meanwhile, the stained area on the modified membrane surface
is much smaller and the color is also lighter. All these should be
owing to quicker penetration of water droplets into the modified
membranes, indicating their better water wettability. In spite of
the high hydrophilicity of the GF membrane itself, its hydrophilic-
ity was further promoted by the HPEI grafting. Among the modified
membranes, the GF-g-HPEI10000 membrane is the least stained.
800 3.4. O/W emulsion filtration
The pure water permeation properties were at first evalu-
ated. At only 10 cm high gravity pressure, pure water flux of
O/N
Si N
47.65 25.81 1.43 33.32
47.25 24.67 1.39 33.99
23.02 10.37 11.22 2.05
20.17 9.59 10.14 1.98
25.86 12.98 8.65 2.99
34 Z. Cao et al. / Chemical Engineering Journal 309 (2017) 30–40

(a) (a’)

(b) (b’)

(c) (c’)

(d) (d’)

Fig. 4. SEM images of the surface morphology of the membranes GF (a, a0 ), GF-g-HPEI60000 (b, b0 ), GF-g-HPEI10000 (c, c0 ) and GF-g-HPEI600 (d, d0 ) (a–d: 2k; a0 –d0 : 30k)
membrane.

the original membrane is about 2600 L/m2h, and those of the should be owing to the increase of membrane hydrophilicity.
modified membrane GF-g-HPEI60000, GF-g-HPEI10000, GF-g- Meanwhile, the trend of flux variation with different mem-
HPEI600 increase to 2700 L/m2h, 2800 L/m2h, and 2800 L/m2h branes is consistent with the dye solution staining results
respectively. The slight increase of pure water permeation flux shown in Fig. 5.
 Z. Cao et al. / Chemical Engineering Journal 309 (2017) 30–40 35

Since the GF-g-HPEI600 membrane has the best permeation and

hydrophilic properties as well as smaller flux variance, it was 1200 100
selected as the representative for O/W emulsion separation. The
O/W separation apparatus and process is shown in Fig. 6. The 1000
80
GF-g-HPEI600 membrane was placed in a dead-end filtration
device. At first, the separation capacity of the membrane for oil dis- 800

J (L/m h)

R (%)
persion without surfactants was evaluated and a n-dodecane/ 60

water oil dispersion was used as the feed. To visualize the O/W
separation, water was stained with methylene blue and n-
dodecyl was stained orange with Sudan I [8,28]. With only gravity
as the only driving force, the water completely permeated through
the membrane, but n-dodecane stayed at top of the membrane
after 24 h. This phenomenon was because of the underwater oleo-
phobic property of membrane [28]. Eventually, rapid separation of
water and n-dodecane was achieved in several seconds, demon-
strating a simple and low cost operation.
Since the composition of oily wastewater is usually very com-
plex, the good separation ability for dispersed oil is insufficient
to meet the requirement by the industrial wastewater treatment.
Therefore, the separation capability of membrane to the emulsified
oil with surfactant added was also evaluated using the SDS stabi-
lized n-dodecane emulsion in water. The oil concentration were
detected by TOC, the data were calculated by the Eq. (2). The
results are shown in Fig. 7. We see that the average emulsion flux
of the original membrane is about 750 L/m2h, and the GF-g-
HPEI60000, GF-g-HPEI10000, GF-g-HPEI600 membranes have
emulsion flux of 900 L/m2h, 1070 L/m2h and 1100 L/m2h respec-
tively. The rejection rate ranges from 99.6 to 99.7% for the GF-g-
HPEI membranes, while that of the unmodified membrane is only
88%. Obviously, the HPEI grafting significantly increases the oil
rejection of the GF membrane. Noted here that the organic content
of filtrate were all less than 20 mg/L.
2
600
40
400
20
200
0 0
GF GF-g-P
GF-g-P
EI6000 EI1000 GF-g-PEI600
0 0
Fig. 7. The emulsion flux (left) and rejection (right) of the GF and modified
membranes.
The water/oil separation was visualized by optical microscopy.
Their droplets are shown in Fig. 8. We prepared four water/oil mix-
ture including hexadecane/water dispersed oil, hexadecane/-
sodium dodecyl sulfate/water emulsions, n-dodecyl/sodium
dodecyl sulfate/water emulsions and soybean oil/sodium dodecyl
sulfate/water emulsions. The average particle diameters of four
water/oil samples were 29.7 lm, 3 lm, 0.9 lm and 0.6 lm, which
fall at the typical size range of oil droplets of oily wastewater. The
optical microscopy images of the feed emulsion and the filtrate are
shown in Fig. 9. We see that the filtrates of the emulsions become
clear and transparent. No oil droplets were observed under micro-
scope except the filtrate of the SDS/soybean O/W emulsion. The

(a) (b) (c) (d)

Fig. 5. Digital photos of the GF (a), GF-g-HPEI60000 (b), GF-g-HPEI10000 (c) and GF-g-HPEI600 (d) membranes with a 10 lL drop on them.

10s 1min 10min 24h

Fig. 6. Images of the O/W separation apparatus equipped with the modified membrane. An oil dispersion was poured into the top glass tube. Water selectively permeated
through the filter, while oil, in orange, was retained on the top. (For interpretation of the references to color in this figure legend, the reader is referred to the web version of
this article.)
36 Z. Cao et al. / Chemical Engineering Journal 309 (2017) 30–40

a Mean 29.728
b Mean 2.973
12
10 S.D. 18.5789 S.D. 1.8579

10
8
8

Frequency(%)
Frequency(%)

6
6

4
4

2 2

0 0
0 10 20 30 40 50 60 70 80 90 1 2 3 4 5 6

Size(μm) Size(μm)

c 12
Mean 0.909 d Mean 0.647
S.D. 0.8894 25
S.D. 0.1615
10

20
8
Frequency(%)

Frequency(%)

15
6

10
4

2 5

0 0
0.5 1.0 1.5 2.0 2.5 3.0 0.2 0.4 0.6 0.8 1.0 1.2 1.4 1.6
Size(μm) Size(μm)

Fig. 8. Droplet size distribution of (a) n-hexadecane /H2O surfactant free emulsion, (b) SDS/n-hexadecane/H2O emulsion, (c) SDS/n-dodecane/H2O emulsion, and (d) SDS/
Soybean oil/H2O emulsion.

(a) before (b) before (c) before (d) before

(a’) aer (b’) aer

(c’) aer (d’) aer

Fig. 9. Optical microscopy images of emulsions before and after GF-g-HPEI600 membrane filtration (Scale bars = 20 lm).
 Z. Cao et al. / Chemical Engineering Journal 309 (2017) 30–40 37

emulsion flux and rejection of the GF-g-PEI600 membrane for fil-

a
tering n-hexadecane/water dispersed oil, n-hexadecane/sodium
1.0
dodecyl sulfate/water emulsions, n-dodecyl/sodium dodecyl sul- GF-g-PEI600
fate/water emulsions are 2100 L/m2h & 99.7%, 1870 L/m2h & GF
PAN
99.7%, 1800 L/m2h & 97%, respectively. As for the soybean oil/- 0.8 PVDFAH

sodium dodecyl sulfate/water emulsion, both flux (930 L/m2h)

Normalized Flux (a.u)

and rejection (72%) are much lower. We see that the filtrate in
0.6
Fig. 9(d0 ) still have a large number of small size oil droplets. The
low rejection for the soybean emulsion can be partially due to
the small particle size of the soybean oil droplets, whose mean par- 0.4
ticle diameter is only 0.647 lm while the pore size of the GF mem-
branes appears to the several micrometers. Besides that, the oil
0.2
wettability on membrane surface also plays a key role on the rejec-
tion performance. Because the soybean oil is more hydrophilic than
the others, it can wet the GF-g-HPEI600 membrane surface more 0.0
easily. As a result, the wetting of the membrane surface overcomes
the capillary pressure that prevents the oil from entering the mem- 0 2 4 6 8 10 12 14 16
brane pores leading to penetration of some oil droplets and low oil
rejection [4]. t (days)
120
b
GF
3.5. The chemical resistance of the modified membrane GF-g-PEI600
110
PAN
PVDF
The composition of real oily emulsions can be very complex and
the membrane may be exposed to extended attack from various 100
solvents. The chemical resistance of the membranes was evaluated
by the soaking treatment with various chemicals including acid, 90
R (%)

base, salt and solvents. The mass loss upon the treatment was
shown in Table 2. We see the membrane shows the highest mass 80
loss in NaOH solution, which should be attributed to SiO2 reacting
with NaOH toward solvable Na2SiO3. Following NaOH, the mass 70
loss rates in different solvents has the order of H2SO4 > H2O2 > -
NaCl > HCl > acetone. H2SO4 and H2O2 cause higher mass loss than 60
others because some adhesive in glass fiber membrane possibly
can be oxidized and leached off by the oxidants. It should be noted
50
that there would not be such an extreme case in the real separation 0 2 4 6 10 15
applications. Therefore, we believe that the modified GF membrane t (days)
have sufficient chemical resistance to various chemicals poten-
tially present in oily waste waters. The membrane surface before Fig. 10. The evolution of emulsion flux (a) and rejection (b) with boiling water
and after treatment was examined using XPS [29]. The elemental treatment for GF, GF-g-HPEI600, PAN and ‘‘PVDFAH” membranes.
composition of the membrane surface before and after soaking
with different solvent was shown in Table 3. We can find that
HCl, acetone and NaCl have little impact on the membrane compo- the membrane also shows dramatic loss on Si content, presumably
sition. As for H2SO4 and H2O2, the decrease of C content and the due to the oxidation of the glass fiber adhesives leading to dra-
increase of O content are obvious, confirming the deterioration of matic increase of the oxygen content, thereafter the decrease of
the membranes due to chemical oxidation. For H2O2 treatment, the Si content. Among all the solvents, NaOH solution causes the

Table 2
The mass loss rates (%) of GF-g-HPEI600 and GF membranes upon treating with different solvents.

Solvent 25% HCl 98%H2SO4 1M NaOH 30% H2O2 Acetone 15% NaCl
GF-g-HPEI600 (%) 1.06 2.94 29.82 2.67 0.59 1.65
GF (%) 1.34 4.61 70.3 4.07 1.47 1.86

Table 3
XPS elemental composition (in at%) of the modified membranes surface before and after soaking with different solvents.

Solvent Element (atom %) O/N Si/N

C O Si N
0 53.47 23.02 10.37 11.22 2.05 0.92
25% HCl 53.16 23.24 10.13 10.7 1.99 0.95
98% H2SO4 49.19 28.43 10.33 10.69 2.66 0.97
1M NaOH 59.46 21.78 6.69 10.49 2.71 0.64
30% H2O2 49.13 32.48 7.94 9.03 3.60 0.88
Acetone 53.83 23.4 10.36 11.08 2.11 0.94
15% NaCl 53.69 23.1 10.32 11.2 2.06 0.92
38 Z. Cao et al. / Chemical Engineering Journal 309 (2017) 30–40
highest decrease on the Si and O content, which confirms the
leaching of SiO2 from the glass fiber. It should be noted that, the
N content of all the membranes is still 10.5% or so after the treat-
ment, indicating the strong bonding of HPEI molecules on the GF
surface. The mass loss rates of the GF membrane were also pro-
vided for comparison. We see the mass loss rates of the GF mem-
brane show the same trend of variation with different solvents
and are all higher than the GF-g-HPEI600 membrane, indicating
that the HPEI grafting layer actually protects the glass underneath
and the mass loss is most attributed to the reaction of solvents
with the pristine glass fibers. Therefore, we conclude that the mod-
ified membrane prepared in this study can be used in harsh condi-
tions with the presence of acids, salts, oxidants, solvents except
strong alkalis.
3.6. The thermal stability of the modified membrane
The good thermal stability of oil emulsion filters not only
ensures its robustness on filtrating emulsions with high tempera-
(a)
(b)
(c)
Fig. 11. SEM images of the (a, a0 ) GF-g-HPEI600, (b, b0 ) PAN and (c, c0 ) ‘‘PVDFAH” membranes before and after boiling treatment for 15 days.
ture, but also facilities high temperature rinsing operations. A long
time boiling treatment was conducted to evaluated membrane
thermal stability. Two typical polymeric membranes, including a
commercial PAN membrane [30] and a membrane made in-
house [10], were used as the control samples. The data of the evo-
lution of emulsion flux and rejection with the water treatment are
shown in Fig. 10. As Fig. 10a shows, the emulsion flux of GF-g-
HPEI600 membrane slightly increase upon the boiling treatment.
On the other hand, the emulsion flux of the other two polymer-
based membranes decreased very quickly with the boiling treat-
ment time. For the PAN membrane, the flux is 29 L/m2h at the start
and became zero after 10 days treatment. For the ‘‘PVDFAH” mem-
brane, the flux was 210 L/m2h at the start, then decreased rapidly
with time, and became zero after 6 days treatment. At the same
time, gradual flux decay was observed for the GF membrane, which
proved the added value of the surface modification on the oil emul-
sion filtration performance. As shown in Fig. 10b, the rejection of
the GF-g-HPEI600 membrane slightly reduced from 99.7% to 97%
with the treatment time increase. The rejection of PAN membrane
(a’)
(b’)
(c’)
 Z. Cao et al. / Chemical Engineering Journal 309 (2017) 30–40
Table 4
XPS elemental composition (in at%) of the PAN and PVDFAH membranes surface before and after boiling treatment for 15 days.
Membranes Element (atom %)
C 1s O 1s
PAN(before) 77.82 4.34
PAN(after) 58.6 20.69
PVDFAH(before) 62.4 17.2
PVDFAH(after) 56.44 6.85
and the ‘‘PVDFAH” membrane were stable at the beginning and
became immeasurable when the emulsion flux became zero. We
note that the rejection of the GF membrane is below 90% during
the whole testing period and were not shown in Fig. 10b.
In order to find out the reason for the different flux evolution
behavior under boiling water treatment, the morphological
changes of the membrane surface was observed by SEM. The mem-
brane surface morphologies before and after 15-days-treatment
were shown in Fig. 11. We see that the porosity increased for the
GF-g-HPEI600 membrane in Fig. 11a, a0 , which may be attributed
to the extraction of the fiber binders with looser fiber packing as
a result. The phenomenon can be used to explain the increase of
the emulsion flux and drop of the oil rejection. In spite of that,
the hydrophilicity of the fiber surface should still be fair so that a
97% oil rejection can be retained. As a comparison, we see from
Fig. 11 (b, b0 ) that the surface functional layer of PAN membrane
suffered from severe damage rendering its support layer exposed.
There are fibers in the non-woven fabric support extruding out of
the surface. We believe that the PAN layer delamination leads to
severe discount of membrane hydrophilicity and then rapid settle-
ment of oil droplets on membrane surface. As a result, the mem-
brane pore is plugged and the emulsion flux became zero. The
same thing should occur to the ‘‘PVDFAH” membrane. We see from
Fig. 11c, c0 that the porous morphology of the ‘‘PVDFAH” mem-
brane was significantly altered with increased porosity as a result
after boiling treatment. However, the expected flux enhancement
was not observed. In contrast, the emulsion flux became zero.
The tethered hydrogel should be leached off during the treatment
leading to permanent loss of surface hydrophilicity. As a result, the
membrane became hydrophobic and were spontaneously wetted
by the emulsified oil during filtration leading to rapid formation
of the cake layer and pore plugging. To testify our speculation on
the damage of PAN layer and leached tethered hydrogel from
PVDFAH membrane, XPS measurements were carried out on the
PAN membrane and PVDFAH membrane before and after the boil-
ing treatment. The evolution of the element content was shown in
Table 4. The significant drop of the carbon and nitrogen content
and the booming of the oxygen content confirms the delamination
of the PAN layer and the exposure of the polyester layer under-
neath. As for the PAVFAH membrane, the drop of the oxygen con-
tent corresponds with the leaching of the crosslinked hydrogel
layer. These results support our conclusion that the boiling treat-
ment causes the delamination of the functional layer leading to
severe decay of the oil emulsion filtration performance. Therefore,
we conclude that the modified GF membrane show the best ther-
mal resistance thanks to its inorganic nature.
4. Conclusion
In this work, a series of superhydrophilic HPEI modified GF
membranes were prepared for oil water separation. Except high
permeation flux (1000 L/m2h under 10 cm gravity pressure) and
quantitative separation (99.7% oil rejection) for water/oil emul-
sions, the modified membranes also exhibit superior chemical
and thermal resistance. Together with the cheap material and the
39
O/N O/C
N S 2p F 1s
17.89 – 0.24 –
10.63 – –
– 2.6 17.8 – 0.28
– 0.75 33.76 – 0.12
versatile fabrication method, the obtained membrane shows
promising potential for robust O/W emulsion separation under
harsh conditions. We believe this report can shed light on the
research of O/W separation. The hydrophilic polymer modified
glass fiber membrane can be a cheap and effective candidate as
water/oil emulsion filters.
Acknowledgements
We gratefully acknowledge support from the National Natural
Science Foundation of China (Grant no. 21574100), the National
Basic Research Program of China (2014CB660813), the National
Natural Science Foundation of China (Grant no. 21274108) and
the Program for Chang-jiang Scholars and Innovative Research
Team in University of Ministry of Education of China (Grant no.
IRT13084).
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