Journal of Applied Polymer Science
Polydopamine Coated PVDF Membrane with High UV-Resistance and Antifouling
Properties for Photocatalytic Membrane Reactor Application
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Polydopamine Coated PVDF Membrane with High UV-Resistance and Antifouling
Properties for Photocatalytic Membrane Reactor Application
Research Article
Syawaliah Muchtar
Mukramah Yusuf Wahab
Li-Feng Fang
Sungil Jeon
Saeid Rajabzadeh, Ph.D
Ryosuke Takagi
Sri Mulyati
Nasrul Arahman
Medyan Riza
Hideto Matsuyama, PhD
Coatings; Membranes; Separation Techniques
Response
Muchtar Syawaliah
Doctoral School of Engineering Science, Syiah Kuala University, Banda Aceh,
Indonesia 23373
Center for Membrane and Film Technology, Graduate School of Engineering, Kobe
University, Rokkodaicho 1-1, Nada, Kobe 657-8501, Japan
May 22, 2018
Dear valued editor;
I send you a manuscript of research paper entitled “Polydopamine Coated PVDF
Membrane with High UV-Resistance and Antifouling Properties for Photocatalytic
Membrane Reactor Application” by M. Syawaliah, H.Matsuyama et al.
In this study PVDF membranes were modified by polydopamine coating for the
membrane photocatalytic application with appropriate UV resistance. The effect of the
PDA coating conditions (i.e., coating time and dopamine concentration), and UV
irradiation time on the modified PVDF membrane properties were studied. The PVDF
membrane surface coated with appropriate dopamine solution concentration and
coating time played a key role in controlling the membrane properties and also
protecting the modified membrane against the UV radiation. Optimizing the coating
condition can not only protect the modified membrane completely far from a free
radical attack initiated by UV irradiation, but also improve the membrane hydrophilicity,
antifouling property, filtration performance and the membrane mechanical strength.
The UV irradiation on the membrane surface coated with high concentration dopamine
solution for long time resulted in the higher mechanical strength than that of the
membrane without the UV irradiation.
I would like to submit this manuscript to Journal of applied polymer scinence. Thank
you for your kind consideration of this manuscript.
 Sincerely yours,
Hideto Matsuyama

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Complete Manuscript

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4 Polydopamine Coated PVDF Membrane with High UV-Resistance and Antifouling Properties
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7 for Photocatalytic Membrane Reactor Application
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11 Syawaliah Muchtar,1,2 Mukramah Yusuf Wahab,1,2 Li-Feng Fang,2,3,4 Sungil Jeon,2 Saeid
12 Rajabzadeh,2 Ryosuke Takagi,2,4 Sri Mulyati,1,5 Nasrul Arahman,1,5 Medyan Riza,1,5 Hideto
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14 Matsuyama2
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17 1 Doctoral School of Engineering Science, Syiah Kuala University, Banda Aceh, Indonesia 23373
18 2
19 Center for Membrane and Film Technology, Graduate School of Engineering, Kobe University,
20 Rokkodaicho 1-1, Nada, Kobe 657-8501, Japan
21 3 Department of Polymer Science and Engineering, Engineering Research Center for Membrane
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23 and Water Treatment, Zhejiang University, Hangzhou 310027, China
24 4 Graduate School of Science, Technology and Innovation, Kobe University, Rokkodaicho 1-1,
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26 Nada, Kobe 657-8501, Japan
27 5 Department of Chemical Engineering, Syiah Kuala University, Banda Aceh, Indonesia 23111
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30 Correspondence to: Hideto Matsuyama (E-mail: matuyama@kobe-u.ac.jp), Sri Mulyati E-mail:
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sri.mulyati@unsyiah.ac.id)
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ABSTRACT
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37 PVDF membranes were modified by polydopamine coating for the membrane photocatalytic
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39 application with appropriate UV resistance. The effect of the PDA coating conditions (i.e.,
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41 coating time and dopamine concentration), and UV irradiation time on the modified PVDF
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43 membrane properties were studied. The PVDF membrane surface coated with appropriate
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dopamine solution concentration and coating time played a key role in controlling the
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47 membrane properties and also protecting the modified membrane against the UV radiation.
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Optimizing the coating condition can not only protect the modified membrane completely far
50 from a free radical attack initiated by UV irradiation, but also improve the membrane
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52 hydrophilicity, antifouling property, filtration performance and the membrane mechanical
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54 strength. The UV irradiation on the membrane surface coated with high concentration
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56 dopamine solution for long time resulted in the higher mechanical strength than that of the
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58 membrane without the UV irradiation.
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INTRODUCTION
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7 In recent years, the photocatalytic membrane reactor has attracted much attention of many
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9 researchers as one of the new emerging advanced wastewater treatment processes.1,2 The
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11 photocatalytic membrane reactor is a hybrid of membrane technology with photo-catalyst to
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13 combine the merits of these two technologies. Photocatalytic membrane reactors are prepared
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by embedding the semiconductor particles such as titanium oxide in the membrane structure.
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17 Energy from light (i.e. visible or UV light) was provided by the photons and absorbed by the
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catalytic particles to start the reaction of the pollutant degradation on the membrane surface.
20 High pollutant degradation performance made this technology as a promising solution to use in
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22 water and wastewater treatment processes.3,4
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25 Although photocatalytic membrane reactors have remarkable advantages, long-term
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27 exposure of the membrane to UV light is the main drawback of the photocatalytic membrane
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29 reactor technology, because it damages the membrane structure and consequently the
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31 membrane performance. Most of the typical materials for membrane preparation such as
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33 polysulfone (PSf), polyethersulfone (PES) and polyvinylidene fluoride (PVDF) are readily
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35 subjected to degradation when they are exposed to UV irradiation for a long time.5-7 If
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37 membrane degradation continues for a while, it will resulted in membrane morphological
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39 damage that leads to decrease in mechanical strength, decreasing membrane separation
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41 performance and shorter service life of the membrane.5,7,8 It is believed that high photon
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43 absorption of the deposited photocatalyst particles resulted in the generation of free radical
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which eventually leads to photodegradation of polymeric membrane through various
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mechanisms such as rearrangement of chemical structure, formation of oxidation products,
48 crosslinking and chain scission reactions.8
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51 One of the practical solutions to overcome this shortcoming is to protect the membrane
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53 surface using compounds that are capable of absorbing and quenching the radicals produced by
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55 UV light.9-13 One of the free radical scavengers that have been recently used is polydopamine
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57 (PDA).11,12,14-18 It is believed that PDA protects the polymeric membrane structure from UV
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59 radiation by quenching the free radicals generated during illumination through electron donor

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reaction.15 This process is possible because PDA is a catechol-bearing compound which is rich in
6 electron-donating hydroxyl and amine groups.19 These groups scavenge free radicals through
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8 intra-molecular hydrogen bonding to stabilize and neutralize them into inactive products like
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10 ROH and H2O.13,15 As far as we know, detail and accurate mechanism of free radical scavenging
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12 activity of PDA to protect membrane have not been studied well and more studies required.
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15 Modification of the membranes by using PDA attracts obvious attention regarding its
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17 super-hydrophilic and adhesion properties. In most cases, PDA was used as an antifouling
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19 agent, and as a medium to stick other components on the membrane surface.20-23 On the other
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21 hand, PDA antioxidation properties were evaluated14,15 and applied in many other fields such as
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23 food science15, plastics24, fiber for clothing16, clay composite17 and so on.
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To the best of our knowledge, PDA has been recently applied as a UV shielding agent
27 11,12
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with the aim of membrane photocatalytic reactor application only in two studies Feng et
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al.11 developed a UV resistance PSf based photocatalytic membrane reactor by coating PDA
31 followed by depositing an amine-functionalized titanium oxide on the deposited PDA layer.
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33 Deposited PDA layer successfully protected the PSf membrane from radical attacks which
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35 resulted in a membrane with satisfactory chemical resistance against UV irradiation and
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37 subsequently stable morphological structure as well as the excellent stability of filtration
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39 performance of the coated membrane compared to that of the pristine membrane. In another
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41 study, Wu et al.12 doped titanium oxide and PDA in nanosphere form into PSf membrane matrix
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43 during the phase separation process. Modified PSf membranes showed outstanding filtration
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45 performance and self-cleaning property over the long time exposure to the UV irradiation.
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47 While outstanding studies were performed by these works, the effect of PDA coating
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49 parameters such as coating time and dopamine concentration was not sufficiently studied in
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51 their published paper.
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In this current study, the effect of the PDA coating conditions (i.e., coating time and
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dopamine concentration), and UV irradiation time on the PVDF membrane properties were
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58 studied. The shielding effect of the coated PDA layer against the free radical attack initiated by
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UV radiation was evaluated based on IR spectra and the mechanical strength retention for

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modified membranes with different coating conditions. Coating conditions played a vital role to
6 obtain a membrane with excellent UV resistance for membrane photocatalytic application. In
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8 addition, PDA coating improved the membrane hydrophilicity and consequently antifouling
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10 properties, and the filtration performance.
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13 EXPERIMENTAL
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Materials
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18 Polyvinylidene fluoride (PVDF) (Solef 6012, Solvay Specialty Polymer, USA) with the molecular
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20 weight of 380,000 was employed as the polymer in membrane fabrication. N,N-
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22 Dimethylacetamide (DMAc) and polyethylene glycol (PEG) (1000 Da, Wako Pure Chemical
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Industries, Japan) were used as a solvent and a pore-forming additive, respectively. Dopamine
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hydrochloride (Sigma Aldrich, Germany) and Tris (2-amino-2-hydroxymethyl-1,3-propanediol)
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28 (Wako Pure Chemical Industries, Japan) were used to prepare dopamine coating solution.
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Bovine serum albumin (BSA) (Wako Pure Chemical Industries, Japan) was used as a model
31 foulant for filtration experiment. Milli-Q water (Milli-Q integral 3, Millipore SAS, France) was
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33 used for a water permeability test and as a solvent in preparing phosphate buffer solution (PBS)
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35 and tris-HCl buffer solution. Meanwhile, deionized (DI) water (Filter Housing PF-3 Organo,
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37 Japan) was used as a non-solvent for membrane fabrication.
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40 Membrane preparation
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42 Preparation of PVDF Membrane
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45 The casting solution was prepared by dissolving 15 g of PVDF and 10 g of PEG1000 into 85 g of
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47 DMAc. The casting solution was stirred vigorously for several hours at 65 ºC to ensure complete
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49 dissolution. After the homogeneous solution was obtained, it was then left to stand for
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51 overnight to eliminate air bubbles which were formed during mixing. The solution was cast on a
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glass plate using a casting blade (Yoshimitsu, Japan) with thickness set at 0.2mm, and then
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immersed into a non-solvent (DI water) bath at 25ºC. The casted glass plate was left in the
56 coagulating bath for about 20 minutes until the membrane spontaneously peeled off
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58 completely from the glass plate. The fabricated membrane was then stored in Milli-Q water
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60 until further use.

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Surface Modification with Polydopamine (PDA)
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7 The preparation of dopamine solution, as well as dip-coating procedure were referred to the
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9 procedure of Vaselbehagh et al. 25 The solution was prepared by dissolving the desired amount
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11 (0.5, 1, and 4 g/L) of dopamine hydrochloride into 15 mM Tris-HCl buffer (pH 8.8). The
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13 membrane was immersed into the freshly prepared dopamine solution for a certain time (i.e 2,
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15 6 and 24 hours). Then, the coated membrane was taken out from the dopamine solution and
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17 rinsed with Milli-Q water and isopropanol alternately for several times to remove the loosely-
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19 attached PDA particles from the membrane surface. The coating conditions are summarized in
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21 Table 1. The coated membranes were denoted according to their respective dopamine
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23 concentration and coating time with the format of ‘dopamine concentration (g/L) - PDA -
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25 coating time (h)’, as shown in Table 1.
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UV Exposure Experiment
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30 The membrane sheet was placed on a plate and put in the hand-made UV irradiation box. The
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32 membrane was set 5 cm under the UV lamp (22W, SUV-16 254nm, AS ONE, Japan). The box was
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34 just the same size as the UV light and was completely closed and sealed. Thus, no light
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36 streamed into the box from outside and UV light did not stream outside. After certain exposure
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38 time, the sample was taken for subsequent characterization.
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41 Characterization of the Membrane
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43 UV Resistance
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46 The UV exposure resistance of pristine PVDF and PDA coated PVDF membranes were evaluated
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48 by the change in IR spectra before and after UV exposure. The IR spectra was measured with
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50 Fourier-Transform Infrared Spectroscopy Attenuated Total Reflectance instrument (FTIR-ATR)
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52 (Thermo Scientific iD5 ATR-Nicolet iS5 FTIR Spectrophotometer, Japan). Prior to IR
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measurement, all the samples were dried in a freeze dryer (FD-1000, Eyela, Japan) for one day
55 to remove water from the membrane.
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58 Membrane Morphology

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The morphology of membrane surface was observed by Field-Emission Scanning Electron
6 Microscopy (FE-SEM, JSF-7500F, Jeol Co. Ltd., Japan). Prior to the measurement, the sample
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8 was dried in a freeze dryer (FD-1000, Eyela, Japan). The sample was coated with osmium coater
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10 (Neoc-STB, Meiwafosis Co. Ltd., Japan) to form an ultra-sized thin osmium layer on the sample.
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13 Mechanical Strength
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16 The mechanical strength of the membrane was evaluated by a tensile strength measured with a
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18 tensile test instrument (Autograph AGS-J, Shimadzu Co., Japan) with reference to ASTM D638-
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20 14. The dimension of test sample was 40mm × 4mm. The thickness of the membrane sample
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22 was measured by a micrometer tool (MCD130-25, Niigataseiki Co., Japan) at least 5 different
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24 random locations. The tension rate was set at 20 mm/min. The tensile strength of five samples
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26 for each membrane ID were measured and the average value was obtained.
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28 Hydrophilicity
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31 The hydrophilicity was evaluated by a water contact angle. Prior to the measurement, the
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33 samples were freeze-dried in a freeze dryer (FD-1000, Eyela, Japan) for overnight. 1 µL of Milli-
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35 Q water was dropped on the membrane surface and the contact angle was measured with a
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37 contact angle meter (Drop Master 300, Kyowa Interface Science Co., Japan).
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40 Pure Water Permeability
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42 The pure water permeability (PWP) of the membrane was measured using a lab-made cross-
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44 flow ultrafiltration cell with an effective area of 9.6 m2 under 1 bar operating pressure and a
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46 feed flow rate of 100 ml/min.26 Prior to the measurement, the membrane was compacted at a
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48 pressure of 1 bar until the Milli-Q water (Milli-Q integral 3, Millipore SAS, France) flux became
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50 stable. The PWP was obtained by Eq. (1)27
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52 Q
53 PWP (1)
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At P
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56 where Q is the quantity of collected permeate (L), A is the effective membrane area (m 2), t is
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58 filtration time (h) and P is the operating pressure (bar).
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Filtration Performance and antifouling properties
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7 Bovine serum albumin (BSA) with a concentration of 1000 ppm (PBS, pH 6.7) was used as a
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9 model foulant to evaluate rejection performance of pristine and PDA coated PVDF before and
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11 after UV irradiation. The procedure and the condition for BSA solution water permeability are
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13 identical to those of pure water permeability. In the case of BSA solution rejection, BSA
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15 concentration of feed and permeate was obtained from the absorbance at 280nm using UV-Vis
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17 Spectrophotometry (U-2000, Hitachi Co., Japan). Eq. (2) was used to calculate the rejection
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19 Cp 
20 R 1 100% (2)
21 Cf 
22

23 where Cp and Cf represent the BSA concentration of permeate and feed, respectively.
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26 The antifouling property was evaluated by Flux Recovery Ratio (FRR). After conducting
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28 initial pure water filtration, the feed was changed to 1000 ppm of BSA in PBS solution. After the
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30 process finished, the used membrane was placed upside down in the UF cell and then milli-Q
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32 water was streamed into the cell at 1 bar for 5 minutes. This membrane was then positioned in
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34 the cell with its original position as during the previous filtration, and the operation was
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continued again on the same membrane by changing the feed to Milli-Q water to obtain the
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second pure water flux. The determination of FRR is given by Eq. (3)
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J
w
FRR 100% (3)
42 J wr 
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44

45 where Jw is the initial water flux before BSA fouling and Jwr is the second water flux after back
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47 flushing.
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56 RESULTS AND DISCUSSION
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59 Chemical Structure Change by PDA Coating and UV Exposure
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PDA deposition on membrane surface was confirmed by IR spectra. Fig. 1a shows the IR spectra
6 of PVDF membranes before and after PDA coating for various concentration and dipping time.
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8 For the transmission spectra of non-coated PVDF, the most specific peaks can be observed at
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10 the wavelength of 3030 and 2980 cm-1 which represent the asymmetric and symmetric
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12 vibration of the C-H band.28 Other particular peaks of PVDF are denoted by the presence of
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14 peaks at the wavenumber of 1403, 1180, 879 and 841 cm -1 which assigned to the C-H wagging
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16 vibration, C-C band, C-C-C asymmetrical and C-F stretching vibrations, respectively.28-30
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19 After PDA coating, the IR spectra shows a new broad peak at spectrum range of 3100 to
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21 3600 cm-1. These peaks attributed to the stretching vibration of N-H and hydroxyl groups from
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23 catechol component which is the major chemical functional group that induces super
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25 hydrophilic characteristic owned by PDA. Also, there are two new distinct peaks detected from
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27 spectra resulted of PDA coated membranes. First one is not so much broad peak related to the
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29 resonance vibration of C=C group from the aromatic ring at a wavelength of 1595 cm-1. This
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peak is attributed the scissoring deformation of the NH2 band. The other peak is resulted from
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the bending vibration of the N-H band from indole groups which emerges at the wavenumber
34 of 1508 cm-1.15,31-33 As shown in Fig. 1a, by increasing the dopamine concentration solution and
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36 coating time, the intensity of the peaks attributed to PDA functional groups increased
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38 considerably due to the increase of PDA amounts deposited on the membrane surface.34,35
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41 To evaluate the effectiveness caused by PDA coating to avoid membrane damage during
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43 the UV exposure, FTIR-ATR was used to analyze the pristine PVDF membrane, and PDA coated
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45 membranes surface after 120h exposure to UV radiation. The results are shown in Fig. 1b and
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47 1c. From Fig. 1b, it is clear that chemical structure of the pristine membrane was changed after
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49 120h exposure to UV radiation. This change in chemical structure can be distinguished by a new
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51 sharp peak at a wavenumber of 1720 cm-1 which appears due to the stretching vibration of the
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53 C=C bond.36 Presumably, this C=C bond appeared on the pristine PVDF UV-irradiated membrane
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55 resulted from the abstraction of hydrogen atoms from C-H chain in PVDF structure by UV-
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57 induced free radicals.36,37 A photon energy (hν) from UV light is strong enough to break polymer
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chemical bonds and produces polymer free radicals. These generated free radicals will react

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with oxygen to form peroxy radicals. By abstracting hydrogen molecule from polymer chain,
6 peroxy radical will form hydroperoxides and more hydrocarbon radicals. If these hydrocarbon
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8 radicals combine with each other, it will resulted in cross-linking, branching, or formation of
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10 low-chained molecular compounds which leads to the change in polymer chemical structure.7,8
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13 On the other hand, Fig. 1c shows that when membrane surface was covered by PDA, the
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15 chemical structure of the coated membrane was not changed even after 120h exposure of UV
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17 light. The high resistance of the PDA coated membrane is attributed to the superior UV-
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19 shielding property of PDA layer which protects the membrane from free radical attack.11,12,15
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21 The shielding effect of the PDA under UV-radiation is attributed to the abundance component
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23 of catecholamine which play a considerable role as free radical quenchers.15 PDA consists of
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25 multi catecholamine chain which is rich in electron-donating hydroxyl groups from phenolic
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27 rings. 9,14,15,38 On the other hand, at the side of each phenolic ring, an amine group exists which
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29 is also an electron donor.15 These groups protect the surface of the membrane by donating
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their hydrogen atoms to bond with free radicals and deactivate them.9,13,15,38 By this scavenging
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mechanism, the radicals will be stopped from abstracting hydrogen from polymer chain and
34 stabilization occurs which eventually leads to the minimization of photodegradation process.13
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36 This is the reason why the PDA coated membrane still has intact chemical structure even after
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38 being exposed to radiation for 120h.
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41 Membrane Morphology Change by PDA Coating and UV Exposure
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44 Effect of PDA coating time and concentration, and UV irradiation time on the outer surface
45 morphology of the modified membranes is shown in Fig. 2. The pristine PVDF membrane
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47 surface shows a smooth surface with some small pores of around hundred nanometers (Fig.
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49 2a). For membrane modified with the shortest coating time (2 hours) and lowest dopamine
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51 solution concentration (0.5 g/L), after membrane modification, membrane surface looks almost
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53 the same as the pristine membrane as shown in Fig. 2b. On the contrary to this, membrane
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55 modified by 24h coating in 4 g/L dopamine solution showed much smaller pores and completely
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57 rough surface with agglomerate of PDA particles (Fig. 2g). It is clear that after PDA coating in
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59 this condition, a layer of PDA film covered membrane surface that resulted in the blocking of

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pores and rough surface with some agglomerated PDA particles. Ho et al.31 reprted that PDA
6 agglomeration happens because during coating process the polymerization of dopamine occurs
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8 not only on the membrane surface, but also in the dopamine solution. The dopamine was
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10 polymerized on the membrane surface as PDA layer and also as aggregated particles in the
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12 solution.
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15 Effect of the UV irradiation on the pristine and modified membranes clearly can be
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17 observed from Fig. 2. It is clear from Fig. 2a and Fig. 2a’ that pristine membrane surface
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19 damaged severely after 120h exposure to the UV radiation. The damage on the membrane
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21 surface is generally in the form of fracture and cracks caused by the attack of free radical
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23 moieties which generated due to the adsorption of photons from UV light during illumination
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25 process.5,24 It is clear that with the increase of dopamine concentration and deposition time,
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27 the deposited amount of the PDA the shielding effect of the PDA increased. Then, the
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29 membrane surface damage induced by the UV radiation decreased sharply. For example, in Fig.
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2g’ (4PDA24), the membrane surface was not changed after UV irradiation. No damaged
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surface of the PDA coated membrane in Fig. 2g’ is attributed to the scavenging activities of PDA
34 layer. However, 0.5 PDA 2, 1 PDA 2 and 4 PDA 2 membranes were still slightly damaged after
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36 UV exposure. It is because at shorter coating time, the deposited layer of PDA was not thick
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38 enough39 which means less PDA functional groups existing on the membrane as previously
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40 verified by the IR results in Fig. 1a. From these results, it can be concluded that deposition
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42 condition (coating time and dopamine concentration) significantly affects the UV resistance of
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44 the prepared membranes.
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47 Mechanical Strength
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49 The mechanical strength of the pristine and modified membranes after the exposure to UV
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51 irradiation were measured. Results were compared with those of the membranes without any
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53 exposure to UV in Fig. 3. The vertical axis indicated the tensile strength retention (%), which is
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55 the tensile strength after UV exposure divided by that before the exposure. It is clear from Fig.
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57 3 that while the tensile strength at break decreased sharply as the UV exposure time increased
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59 for pristine PVD membrane, this tensile strength decrease was prevented by increasing the PDA

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concentration and coating time. When membrane was modified with the dopamine solution at
6 low concentration (i.e., 0.5 g/L), the coating time affected the membrane mechanical strength
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8 against the UV exposure. It means that the more prolonged the deposition time was, the
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10 stronger the membrane against UV exposure was. On the contrary to the low PDA
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12 concentration, when PDA concentration increased to 4 g/L, even short time PDA deposition was
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14 enough to obtain a perfect UV resistant membrane.
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17 Mechanical strength results shown in Fig. 3 agrees very well with the SEM images shown
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19 in Fig. 2. When cracks and fractures observed on the outer surface of the membrane (Fig. 2a’),
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21 the membrane mechanical strength decreased sharply. By decreasing the cracks and fractures
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23 size on the membrane surface, membrane mechanical strength retention increased. It is
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25 noteworthy to mention here that the formation of cracks and fractures are very influential on
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27 the tensile properties as they lead to the embrittlement of the membrane.24,40 Embrittlement
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29 of membrane progresses gradually over UV exposure time, initially took place at the surface of
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the polymeric membrane and eventually to whole membrane matrix after long time exposure
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to UV radiation.5,24 During the tensile strength test, cracks formed on the membrane surface
34 will expand and propagate to the interior parts of the membrane. 24 White and Rabello40
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36 reported that at a short UV exposure time, the irradiated polymer still has a non-degraded
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38 ductile layer underneath the degraded surface. This layer avoids the fast propagation of cracks,
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40 and consequently, the decrease in mechanical strength would be marginal. With further
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42 increase in UV exposure time, cracks and fractures progress all over the membrane matrix and
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44 make the membrane entirely brittle.
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47 It is interesting to see that after UV exposure, some PDA coated membranes (e.g., 4
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49 PDA24 membrane) show mechanical strength even higher than that of the membrane without
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51 UV exposure. If the coated PDA acts only as a shielding agent with free radical scavenging
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53 groups to keep membrane out of free radicals attack, it is expected that membrane mechanical
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55 strength would be the same as before UV exposure. Therefore, some other mechanisms play a
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57 role in the improving membrane mechanical strength. PDA is known as bio-inspired glue due to
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its adhesion characteristic.19 Herein PDA adhesive property played a role as a binder to increase

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the membrane mechanical strength by improving the interconnected structure of the
6 membrane network.16,41 We presume that the UV irradiation could somehow enhance binding
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8 interaction between PDA layer and membrane surface through some kind of UV-triggered
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10 cross-linking interaction, which makes the membrane completely tough. The phenomena
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12 related to this increment in membrane mechanical strength is not completely clear and more
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14 basic research is needed to understand it clearly. As a brief conclusion for the results shown in
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16 Fig. 3, modified PVDF membrane with optimal PDA coating time and concentration, not only
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18 membrane mechanical strength will not decrease during the UV radiation, but also it can
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20 increase the membrane mechanical strength higher than the original one.
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23 Membrane Hydrophilicity and Pure Water Permeability
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25 Contact angle measurement results are shown in Fig.4a. Fig.4a clearly shows that by increasing
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27 the coating time and dopamine concentration, the membrane water contact angle decreased
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29 and therefore it can be concluded that the membrane surface hydrophilicity increased. The
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31 increase in hydrophilicity of the coated membrane is attributed to the presence of
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33 catecholamine (N-H and O-H) functional groups on PDA layer31,32 as explained in the section
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35 membrane morphology change by PDA coating and UV exposure. The existence of these groups
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37 enhanced the interaction between water molecules and membrane surface 32 which is
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39 favorable to increase the membrane water permeability and reducing fouling propensity. It
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41 looks that for the range of PDA concentration and coating time in this study, coating time was
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43 more effective than that the PDA solution concentration. By using 4 g/L dopamine solution and
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24 hours coating time, membrane contact angle decreased from 72º to 50º, while the contact
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angle decreased from 72º to 61º by using 4 g/L dopamine solution and 2hours coating time.
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49 Figure 4b shows the results for pure water permeability of the coated membranes and
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51 pristine PVDF. When PVDF membrane immersed in PDA solution for not so long time (2 and 6
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53 hours), pure water permeability increased to be higher than that of the pristine membrane. For
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55 longer coating time (24 hours), the membrane pure water permeability decreased sharply. The
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57 same phenomenon was observed in similar studies from different research groups.39,41 It might
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59 be explained as follows. When the coating time is short, only a thin layer of PDA can be coated

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on the membrane surface. Although the membrane surface pore size decreases slightly,
6 membrane surface hydrophilicity increases, as shown in Fig. 4a. The effect of the surface
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8 hydrophilicity improvement may be predominant, compared with that of pore size decrease,
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10 which leads to the enhancement of the pure water permeability. By further increase in the
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12 membrane coating time, membrane hydrophilicity increases slightly more (as shown in Fig. 4a),
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14 while the membrane surface will be covered by a thick layer of PDA layer or PDA aggregates
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16 that blocks the membrane surface pores as shown in Fig. 2. Thus, the sharp decrease in pure
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18 water permeability occurred.
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21 For practical applications of the membrane, it is vital to improve all the characteristics of
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23 the membrane to a certain satisfying level. Considering the prepared membranes
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25 hydrophilicity, pure water permeability and UV resistance for different coating time and
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27 dopamine solution concentrations, trade off behavior can be observed from results shown in
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29 Fig. 3 and Fig. 4. Higher pure water permeability, acceptable improvement in hydrophilicity and
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31
UV resistance obtained when low PDA concentration (0.5 g/L) was used for membrane coating.
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33
On the other hand, high UV resistance and hydrophilicity with moderate pure water
34 permeability were obtained when a high concentration of PDA (4 g/L) was used for membrane
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36 modification. Based on these results, using 1g/L dopamine solution will result in the modified
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38 membranes with optimal membrane properties including hydrophilicity, pure water
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40 permeability and UV resistance. Thus, for the following membrane assessments, only
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42 membranes coated with dopamine solution with 1g/L concentration will be considered.
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45 BSA Filtration Performance of the Modified Membranes
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48 BSA filtration performance of the PDA coated membranes before and after UV exposure were
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50 evaluated and results are compared with those of the pristine PVDF membrane in Fig. 5a and
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52 Fig. 5b. Fig. 5a shows that water permeability of the pristine PVDF membrane is low (15 Lm-2h-
53 1bar-1)
54 and it reaches to the maximum value for the membrane coated in PDA for 2 hours (39
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Lm-2h-1bar-1) in no UV exposure condition. The longer coating time (6 and 24 hours) brought
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58 about the subsequent decrease of water permeability (21-23 Lm-2h-1bar-1) . This trend might be
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explained as follow. Pristine PVDF membrane water permeability is completely low because it is

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hydrophobic and BSA solution makes a severe fouling in membranes as soon as filtration
6 process starts.42 Thus, it is reasonable to have a low water permeability for BSA filtration. The
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8 pure water permeability of the 1PDA2 membrane (coated for 2 hours in 1g/L dopamine
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10 solution) is the highest among all the prepared membranes because the membrane is not so
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12 much hydrophobic (Fig.4a) and also membrane pores were not blocked tightly by PDA
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14 deposition. Thus, it is expected to obtain a membrane with high water permeability and similar
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16 BSA rejection to the pristine membrane (88%) as shown in Fig 5b. Further increase in coating
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18 time, resulted in membranes with smaller pore size and lowered the water permeability.
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21 Figure 5a shows that the difference between the water permeability of the coated
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23 membranes before and after UV exposure is not significant (less than 10%), while this
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25 difference is strongly noticeable (almost 100%) for pristine membrane. This difference easily
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27 can be addressed by considering that PVDF membrane surface damaged severely by the
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29 formation of cracks and fractures, since it cannot be protected by a coated PDA layer.
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31
Therefore, water permeability increased sharply from 15 to 29 Lm-2h-1bar-1 and BSA rejection
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33
decreased noticeably from 87% to 67% (Fig.5b) due to the increase in membrane pore size. It is
34 worth to mention here that only for one membrane (1PDA24 membrane), the water
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36 permeability decreased slightly after UV exposure. It means UV irradiation not only affects the
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38 membrane structure, but also makes membrane surface denser. As described above, the
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40 mechanical strength retention of the membrane coated with longest coating time was higher
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42 after UV exposure than that of the membrane without UV exposure, probably due to the UV-
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44 triggered cross-linking formation. The data of decreased water permeability agrees with this
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46 result of mechanical strength retention.
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48
49 Antifouling properties
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52 As another essential assessment of the prepared membranes, the antifouling propensity of the
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54 prepared membranes were evaluated by performing pure water permeation again after
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56
backflushing. The results were reported in terms of flux recovery ratio (FRR) which is good
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58 indication for membrane fouling recovery after backwashing.43 The results of FRR for modified
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membranes and pristine PVDF membrane before and after UV exposure, are shown in Fig. 6.

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Among all the membranes, PVDF pristine membrane showed the least FRR due to the
6 hydrophobic nature of the PVDF.44 After UV irradiation, the FRR of pristine membrane further
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8 reduced to 56%, which is related to the enlargement of the pore size due to UV exposure which
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10 leads to the accelerating deposition of BSA molecules inside the membrane pores. 5,45 As shown
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12 in Fig.6, by increasing PDA coating time, FRR increased from 66% for pristine PVDF membrane
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14 to 86% for 1PDA24 membrane. The FRR of modified membranes remained almost the same
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16 even after 120h UV exposure. It can be concluded that coating modification of the PVDF
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18 membrane with coating time longer than 6 hours was effective to improve the antifouling
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20 properties, and UV exposure had almost no effect on the FRR.
21
22
23 CONCLUSIONS
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25 The super-hydrophilic polymer, PDA coating, was attempted to make an appropriate
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27 membrane for photocatalytic reactor membrane with strong resistance against the UV
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29 radiation. PDA solution concentration and coating time played a key role to control the
30
31 membrane properties including UV resistance, hydrophilicity, filtration performance and also
32
33 membrane mechanical strength. Based on obtained results, 1 g/L PDA solution concentration
34
35 with more than 6 hours coating time was an optimal condition to obtain a membrane with high
36
37 water permeability, acceptable BSA rejection, good antifouling properties, excellent UV
38
39 resistance and mechanical strength.
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41 Our next target is a preparation of the photocatalytic membrane by embedding the
42
43 semiconductor particles, based on the kowledge on the UV resistence property of the base
44
45
polymer membrane obtained in this work.
46
47 ACKNOWLEDGEMENTS
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49
50 The activity of this collaboration research was financially supported by the Ministry of Research,
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52 Technology and Higher Education of the Republic of Indonesia under ‘PMDSU’ scholarship
53
54 through ‘Sandwich-like PKPI’ program.
55
56
57
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59 TABLE AND FIGURES
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4 Table 1 Membrane Coating Conditions
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7 PDA Coating Conditions

8 Membrane ID
Dopamine Concentration Coating Time
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(g/L) (hours)
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11 PVDF 0 0
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13 0.5 PDA 2 0.5 2
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15 0.5 PDA 6 0.5 6
16
0.5 PDA 24 0.5 24
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18 1 PDA 2 1 2
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20 1 PDA 6 1 6
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1 PDA 24 1 24
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23 4 PDA 2 4 2
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25 4 PDA 6 4 6
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27 4 PDA 24 4 24
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49 Figure 1 IR spectra of (a) pristine PVDF membrane before and after PDA coating with different dopamine
50 concentration and coating time, (b) Pristine PVDF membranes before and after 120h of UV exposure,
51
and (c) PDA coated PVDF membranes before and after 120h of UV exposure
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58 Figure 2 FE-SEM images of original and PDA-coated PVDF membranes of different concentration and coating time before UV exposure (a-g) and
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60 after 120h of UV exposure (a’-g’)
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33 Figure 3 Tensile strength retention of the different membranes coated with different dopamine
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35 concentration and coating time
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56 Figure 4 Effects dopamine concentration and coating time on (a) water contact angle and (b) Pure Water
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Permeability of PVDF membrane
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57 Figure 5 BSA solution (a) water permeability and (b) rejection performance of original PVDF membrane
58 and PVDF coated with 1 g/L dopamine at different coating time, before and after 120 h of UV irradiation
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34 Figure 6 Flux Recovery Ratio of original PVDF membrane and PVDF coated with 1 g/L dopamine at
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Graphical Abstract Image